3-Heterocyclyl substituted benzoic acid derivatives

ABSTRACT

Disclosed are 3-heterocyclyl substituted benzoic acid derivatives of general formula (I), 
                         
in which the variables R 1  to R 8  and X have the meanings indicated in claim  1,  and the use thereof as herbicides or for desiccating/defoliating plants.

CROSS REFERENCE TO RELATED APPLICATION

This application is a 35 USC §371 National Phase Entry Application from PCT/EP2003/008013, filed Jul. 22, 2003, and designating the U.S.

The present invention relates to 3-heterocyclyl-substituted benzoic acid derivatives and their agriculturally useful salts, to compositions comprising such compounds and to the use of the 3-heterocyclyl-substituted benzoic acid derivatives, of their salts or of compositions comprising them as herbicides, desiccants or defoliants.

In various publications, uracil-substituted benzoic acid derivatives have been described as herbicidally active compounds. Thus, for example, WO 88/10254, WO 89/03825 and WO 91/00278 describe the esters of 2-halo-5-(substituted uracil)benzoic acids and the esters of 2-cyano-5-(substituted uracil)benzoic acids which may optionally be halogen-substituted in the 4-position. WO 89/02891 and WO 93/06090 describe the amides of 2-halo-5-(substituted uracil)benzoic acids and the amides of 2-cyano-5-(substituted uracil)benzoic acids which may optionally be halogen-substituted in the 4-position, as herbicidally active substances.

Furthermore, WO 01/83459 discloses herbicidally active 3-heterocyclyl-substituted phenylsulfamoylcarboxamides of the formula A

where Het is, inter alia, an unsaturated five- or six-membered heterocyclic radical which is attached via a nitrogen atom to the phenyl ring, X¹ is hydrogen, halogen or C₁-C₄-alkyl, X² is hydrogen, cyano, thiocarbamoyl, halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl, X³ is, inter alia, hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxyalkyl, R′ are each independently of one another inter alia hydrogen, alkoxy, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-alkynyl, C₃-C₇-cycloalkyl, or the two radicals R′ together with the nitrogen atom to which they are attached form a 3- to 7-membered heterocyclic ring.

It is an object of the present invention to provide novel herbicidally active compounds which allow better targeted control of unwanted plants than the known herbicides. Advantageously, the novel herbicides should be highly active against harmful plants. Moreover, a high compatibility with crop plants is desirable. It is another object to provide novel compounds having desiccant/defoliant action.

We have found, surprisingly, that these objects are achieved by 3-heterocyclyl-substituted benzoic acid derivatives of the general formula I defined below:

where:

-   X is oxygen or NR⁹, -   R¹ is a heterocyclic radical of the formulae II-A to II-H,

-   R² is hydrogen or halogen, -   R³ is halogen or cyano, -   R⁴, R⁵ independently of one another are hydrogen, C₁-C₄-alkyl or     C₁-C₄-alkoxy, or R⁴ and R⁵ together are a group ═CH₂, -   R⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, -   R⁷, R⁸ independently of one another are hydrogen, C₁-C₆-alkyl,     C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₄-haloalkyl,     C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl,     C₁-C₄-alkylsuifinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl,     cyano-C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl-C₁-C₄-alkyl,     amino-C₁-C₄-alkyl, C₁-C₄-alkylamino-C₁-C₄-alkyl,     di(C₁-C₄-alkyl)amino-C₁-C₄-alkyl, aminocarbonyl-C₁-C₄-alkyl,     (C₁-C₄-alkylamino)carbonyl-C₁-C₄-alkyl,     di(C₁-C₄-alkyl)aminocarbonyl-C₁-C₄-alkyl, phenyl or     C₁-C₄-alkylphenyl or -   R⁷ and R⁸ together with the nitrogen atom to which they are attached     form a saturated or unsaturated 3-, 4-, 5-, 6- or 7-membered     nitrogen heterocycle which may optionally contain one or two further     heteroatoms selected from the group consisting of nitrogen, sulfur     and oxygen as ring members, which may contain 1 or 2 carbonyl and/or     thiocarbonyl groups as ring members and/or which may be substituted     by one, two or three substituents selected from the group consisting     of C₁-C₄-alkyl and halogen; -   R⁹ is hydrogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy, phenyl,     phenyl-C₁-C₄-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, -   R¹⁰ is hydrogen, C₁-C₄-alkyl or amino, -   R¹¹ is C₁-C₄-alkyl or C₁-C₄-haloalkyl, -   R¹² is hydrogen or C₁-C₄-alkyl, -   R¹³, R^(13′) independently of one another are hydrogen or     C₁-C₄-alkyl, -   R¹⁴ is halogen, -   R¹⁵ is hydrogen or C₁-C₄-alkyl, -   R¹⁶ is C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl or     C₁-C₄-alkylsulfonyloxy, -   R¹⁷ is hydrogen or C₁-C₄-alkyl, -   R¹⁸ is hydrogen, C₁-C₄-alkyl or amino, -   R¹⁹ is C₁-C₄-haloalkyl, C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl. -   R²⁰ is hydrogen or C₁-C₄-alkyl, -   R²¹ is hydrogen, halogen or C₁-C₄-alkyl, -   R²² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy,     C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl, -   R²³ is hydrogen or C₁-C₄-alkyl,     or -   R²² and R²³ together with the atoms to which they are attached form     a 5-, 6- or 7-membered saturated or unsaturated ring which may     contain a heteroatom selected from the group consisting of oxygen     and nitrogen as a ring-forming atom and/or which may be substituted     by one, two or three radicals selected from the group consisting of     C₁-C₄-alkyl and halogen, -   R²⁴ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl, -   R²⁵ is C₁-C₄-alkyl or C₁-C₄-haloalkyl,     or -   R²⁴ and R²⁵ together with the atoms to which they are attached form     a 5-, 6- or 7-membered saturated or unsaturated ring which     optionally contains an oxygen atom as ring-forming atom and/or which     may be substituted by one, two or three radicals selected from the     group consisting of C₁-C₄-alkyl and halogen, -   R²⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl, -   R²⁷ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,     or -   R²⁶ and R²⁷ together with the atoms to which they are attached form     a 5-, 6- or 7-membered saturated or unsaturated ring which     optionally contains an oxygen atom as ring-forming atom and/or which     may be substituted by one, two or three radicals selected from the     group consisting of C₁-C₄-alkyl and halogen, -   A¹, A², A³, A⁴ are each independently of one another oxygen or     sulfur.

Accordingly, the present invention relates to 3-heterocyclyl-substituted benzoic acid derivatives of the formula I and their agriculturally useful salts.

The invention also relates to the tautomers of the compounds I, for example to compounds I in which R¹ is a heterocyclic radical of the formula II-A, II-B, II-F or II-H.

Moreover, the present invention relates to

-   -   the use of the compounds I and/or their salts as herbicides or         for the desiccation/defoliation of plants     -   herbicidal compositions comprising the compounds I and/or their         salts as active substances,     -   compositions for the dessication/defoliation of plants, which         compositions comprise the compounds I and/or their salts as         active substances, and also     -   methods for controlling unwanted vegetation or for the         desiccation/defoliation of plants using the compounds I and/or         their salts.

Depending on the substitution pattern, the compounds of the formula I may contain one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or diastereomers and mixtures thereof.

Agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the herbicidal action and/or desiccant/defoliant action of the compounds I. Thus, particularly suitable cations are the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion, which, if desired, may carry one to four C₁-C₄-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, hydrogencarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The organic moieties mentioned in the definition of the substituents R¹ to R²⁷ or as radicals on heterocyclic rings are—like the term halo—collective terms of individual listings of the individual group members. All carbon chains, i.e. all alkyl, haloalkyl, cyanoalkyl, aminoalkyl, aminocarbonylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy and alkenyl moieties may be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms. The term halogen denotes in each case fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

-   -   C₁-C₄-alkyl: for example methyl, ethyl, propyl, 1-methylethyl,         butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;     -   C₁-C₆-alkyl: C₁-C₄-alkyl as mentioned above and also, for         example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,         2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl,         1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,         3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,         1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,         2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,         2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl or         1-ethyl-3-methylpropyl;     -   C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which         is partially or fully substituted by fluorine, chlorine, bromine         and/or iodine, i.e., for example, chloromethyl, dichloromethyl,         trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,         chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,         2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,         2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,         2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,         2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl,         3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,         2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl,         2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,         3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl,         heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl,         1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,         4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;         in particular difluoromethyl, trifluoromethyl;     -   C₁-C₄-alkoxy: for example methoxy, ethoxy, n-propoxy,         1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or         1,1-dimethylethoxy;     -   C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above         which is partially or fully substituted by fluorine, chlorine,         bromine and/or iodine, i.e. for example, OCH₂F, OCHF₂, OCF₃,         OCH₂Cl, OCH(Cl)₂, OC(Cl)₃, chlorofluoromethoxy,         dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy,         2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy,         2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,         2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,         2,2,2-trichloroethoxy, OC₂F₅, 2-fluoropropoxy, 3-fluoropropoxy,         2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy,         3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy,         3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,         OCH₂—C₂F₅, OCF₂—C₂F₅, 1-(CH₂F)-2-fluoroethoxy,         1-(CH₂Cl)-2-chloroethoxy, 1-(CH₂Br)-2-bromoethoxy,         4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or         nonafluorobutoxy, preferably OCHF₂;     -   C₁-C₄-alkoxy-C₁-C₄-alkyl: C₁-C₄-alkyl which is substituted by         C₁-C₄-alkoxy as mentioned above, i.e., for example, CH₂—OCH₃,         CH₂—OC₂H₅, n-propoxymethyl, CH₂—OCH(CH₃)₂, n-butoxymethyl,         (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, CH₂—OC(CH₃)₃,         2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl,         2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl,         2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl,         2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl,         2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl,         2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl,         2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl,         3-(methoxy)propyl, 3-(ethoxy)propyl, 3-(n-propoxy)propyl,         3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl,         3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl,         3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl,         2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl,         2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl,         2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl,         3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl,         3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl,         3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl,         4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl,         4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or         4-(1,1-dimethylethoxy)butyl;     -   C₁-C₄-alkylthio: for example SCH₃, SC₂H₅, SCH₂—C₂H₅, SCH(CH₃)₂,         n-butylthio, SCH(CH₃)—C₂H₅, SCH₂—CH(CH₃)₂ or SC(CH₃)₃;     -   C₁-C₄-alkylthio-C₁-C₄-alkyl: C₁-C₄-alkyl, which is substituted         by C₁-C₄-alkylthio as mentioned above, i.e., for example,         CH₂—SCH₃, CH₂—HC₂H₅, n-propylthiomethyl, CH₂—SCH(CH₃)₂,         n-butylthiomethyl, (1-methylpropylthio)methyl,         (2-methylpropylthio)methyl, CH₂—SC(CH₃)₃, 2-(methylthio)ethyl,         2-(ethylthio)ethyl, 2-(n-propylthio)ethyl,         2-(1-methylethylthio)ethyl, 2-(n-butylthio)ethyl,         2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl,         2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl,         2-(ethylthio)propyl, 2-(n-propylthio)propyl,         2-(1-methylethylthio)propyl, 2-(n-butylthio)propyl,         2-(1-methylpropylthio)propyl, 2-(2-methylpropylthio)propyl,         2-(1,1-dimethylethylthio)propyl, 3-(methylthio)propyl,         3-(ethylthio)propyl, 3-(n-propylthio)propyl,         3-(1-methylethylthio)propyl, 3-(n-butylthio)propyl,         3-(1-methylpropylthio)propyl, 3-(2-methylpropylthio)propyl,         3-(1,1-dimethylethylthio)propyl, 2-(methylthio)butyl,         2-(ethylthio)butyl, 2-(n-propylthio)butyl,         2-(1-methylethylthio)butyl, 2-(n-butylthio)butyl,         2-(1-methylpropylthio)butyl, 2-(2-methylpropylthio)butyl,         2-(1,1-dimethylethylthio)butyl, 3-(methylthio)butyl,         3-(ethylthio)butyl, 3-(n-propylthio)butyl,         3-(1-methylethylthio)butyl, 3-(n-butylthio)butyl,         3-(1-methylpropylthio)butyl, 3-(2-methylpropylthio)butyl,         3-(1,1-dimethylethylthio)butyl, 4-(methylthio)butyl,         4-(ethylthio)butyl, 4-(n-propylthio)butyl,         4-(1-methylethylthio)butyl, 4-(n-butylthio)butyl,         4-(1-methylpropylthio)butyl, 4-(2-methylpropylthio)butyl or         4-(1,1-dimethylethylthio)butyl;     -   C₁-C₄-alkylsulfinyl (C₁-C₄-alkyl-S(═O)—) and the alkylsulfinyl         moieties of C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl: for example         methylsulfinyl, ethylsulfinyl, propylsulfinyl,         1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl,         2-methylpropylsulfinyl or 1,1-dimethylethylsulfinyl;     -   C₁-C₄-alkylsulfonyl (C₁-C₄-alkyl-S(═O)₂—) and the alkylsulfonyl         moieties of C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl: for example         methylsulfonyl, ethylsulfonyl, propylsulfonyl,         1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl,         2-methylpropylsulfonyl or 1,1-dimethylethylsulfonyl, preferably         methylsulfonyl;     -   C₁-C₄-alkylsulfonyloxy: for example methylsulfonyloxy,         ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy,         butylsulfonyloxy, 1-methylpropylsulfonyloxy,         2-methylpropylsulfonyloxy or 1,1-dimethylethylsulfonyloxy,         preferably methylsulfonyloxy;     -   cyano-C₁-C₄-alkyl: for example CH₂CN, 1-cyanoethyl,         2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl,         3-cyanoprop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl,         3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl,         2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl,         1-(CH₂CN)eth-1-yl, 1-(CH₂CN)-1-(CH₃)eth-1-yl or         1-(CH₂CN)prop-1-yl;     -   phenyl-C₁-C₄-alkyl: for example benzyl, 1-phenylethyl,         2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl,         3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl,         3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl,         2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl,         1-(benzyl)eth-1-yl, 1-(benzyl)-1-(methyl)eth-1-yl or         1-(benzyl)prop-1-yl;     -   C₁-C₄-alkoxycarbonyl: for example methoxycarbonyl,         ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl,         butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl         or 1,1-dimethylethoxycarbonyl;     -   (C₁-C₄-alkoxy)carbonyl-C₁-C₄-alkyl: C₁-C₄-alkyl which is         substituted by (C₁-C₄-alkoxy)carbonyl as mentioned above, i.e.,         for example, CH₂—CO—OCH₃, CH₂—CO—OC₂H₅, CH₂—CO—OCH₂—C₂H₅,         CH₂—CO—OCH(CH₃)₂, n-butoxycarbonylmethyl, CH₂—CO—OCH(CH₃)—C₂H₅,         CH₂—CO—OCH₂—CH(CH₃)₂, CH₂—CO—OC(CH₃)₃, 1-(CO—OCH₃) ethyl,         1-(CO—OC₂H₅) ethyl, 1-(CO—OCH₂—C₂H₅)ethyl,         1-[CO—OCH(CH₃)₂]ethyl, 1-(n-butoxycarbonyl)ethyl,         1-[1-methylpropoxycarbonyl]ethyl,         1-[2-methylpropoxycarbonyl]ethyl, 2-(CO—OCH₃)ethyl, 2-(CO—OC₂H₅)         ethyl, 2-(CO—OCH₂—C₂H₅) ethyl, 2-[CO—OCH(CH₃)₂]ethyl,         2-(n-butoxycarbonyl)ethyl, 2-[1-methylpropoxycarbonyl]ethyl,         2-[2-methylpropoxycarbonyl]ethyl, 2-[CO—OC(CH₃)₃]ethyl,         2-(CO—OCH₃)propyl, 2-(CO—OC₂H₅)propyl, 2-(CO—OCH₂—C₂H₅) propyl,         2-[CO—OCH(CH₃)₂]propyl, 2-(n-butoxycarbonyl) propyl,         2-[1-methylpropoxycarbonyl]propyl,         2-[2-methylpropoxycarbonyl]propyl, 2-[CO—OC(CH₃)₃]propyl,         3-(CO—OCH₃) propyl, 3-(CO—OC₂H₅)propyl, 3-(CO—OCH₂—C₂H₅) propyl,         3-[CO—OCH(CH₃)₂]propyl, 3-(n-butoxycarbonyl)propyl,         3-[1-methylpropoxycarbonyl]propyl,         3-[2-methylpropoxycarbonyl]propyl, 3-[CO—OC(CH₃)₃]propyl,         2-(CO—OCH₃)butyl, 2-(CO—OC₂H₅)butyl, 2-(CO—OCH₂—C₂H₅)butyl,         2-[CO—OCH(CH₃)₂]butyl, 2-(n-butoxycarbonyl)butyl,         2-[1-methylpropoxycarbonyl]butyl,         2-[2-methylpropoxycarbonyl]butyl, 2-[CO—OC(CH₃)₃]butyl,         3-(CO—OCH₃)butyl, 3-(CO—OC₂H₅)butyl, 3-(CO—OCH₂—C₂H₅)butyl,         3-[CO—OCH(CH₃)₂]butyl, 3-(n-butoxycarbonyl)butyl,         3-[1-methylpropoxycarbonyl]butyl,         3-[2-methylpropoxycarbonyl]butyl, 3-[CO—OC(CH₃)₃]butyl,         4-(CO—OCH₃)butyl, 4-(CO—OC₂H₅)butyl, 4-(CO—OCH₂—C₂H₅)butyl,         4-[CO—OCH(CH₃)₂]butyl, 4-(n-butoxycarbonyl)butyl,         4-[1-methylpropoxycarbonyl]butyl,         4-[2-methylpropoxycarbonyl]butyl or 4-[CO—OC(CH₃)₃]butyl,         preferably CH₂—CO—OCH₃, CH₂—CO—OC₂H₅, 1-(CO—OCH₃) ethyl or         1-(CO—OC₂—H₅) ethyl;     -   amino-C₁-C₄-alkyl: for example CH₂NH₂, 1-aminoethyl,         2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl,         3-aminoprop-1-yl, 1-aminobut-1-yl, 2-aminobut-1-yl,         3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl,         2-aminobut-2-yl, 3-aminobut-2-yl, 4-aminobut-2-yl, 1-(CH₂NH₂)         eth-1-yl, 1-(CH₂NH₂)-1-(CH₃) eth-1-yl or 1-(CH₂NH₂) prop-1-yl;     -   C₁-C₄-alkylamino: for example H₃C—NH—, H₅C₂—NH—, n-propyl-NH—,         1-methyl ethyl-NH-, n-butyl-NH-, 1-methylpropyl-NH-,         2-methylpropyl-NH— or 1,1-dimethylethyl-NH—;     -   C₁-C₄-alkylamino-C₁-C₄-alkyl: C₁-C₄-alkyl which is substituted         by C₁-C₄-alkylamino as defined above, i.e., for example,         CH₂CH₂—NH—CH₃, CH₂CH₂—N(CH₃)₂, CH₂CH₂—NH—C₂H₅ or         CH₂CH₂—N(C₂H₅)₂;     -   di(C₁-C₄-alkyl)amino: N(CH₃)₂, N(C₂H₅)₂, N,N-dipropylamino,         N,N-di(1-methylethyl)amino, N,N-dibutylamino,         N,N-di(1-methylpropyl)amino, N,N-di-(2-methylpropyl)amino,         N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino,         N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino,         N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino,         N-methyl-N-(2-methylpropyl)amino,         N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino,         N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino,         N-ethyl-N-(1-methylpropyl)amino,         N-ethyl-N-(2-methylpropyl)amino,         N-ethyl-N-(1,1-dimethylethyl)amino,         N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino,         N-(1-methylpropyl)-N-propylamino,         N-(2-methylpropyl)-N-propylamino,         N-(1,1-dimethylethyl)-N-propylamino,         N-butyl-N-(1-methylethyl)amino,         N-(1-methylethyl)-N-(1-methylpropyl)amino,         N-(1-methylethyl)-N-(2-methylpropyl)amino,         N-(1,1-dimethylethyl)-N-(1-methylethyl)amino,         N-butyl-N-(1-methylpropyl)amino,         N-butyl-N-(2-methylpropyl)amino,         N-butyl-N-(1,1-dimethylethyl)-amino,         N-(1-methylpropyl)-N-(2-methylpropyl)amino,         N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino or         N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino;     -   di(C₁-C₄-alkyl)amino-C₁-C₄-alkyl: C₁-C₄-alkyl which is         substituted by di(C₁-C₄-alkyl)amino as mentioned above, i.e.,         for example, CH₂N(CH₃)₂, CH₂N(C₂H₅)₂, N,N-dipropylaminomethyl,         N,N-di[CH(CH₃)₂]aminomethyl, N,N-dibutylaminomethyl,         N,N-di(1-methylpropyl)aminomethyl,         N,N-di(2-methylpropyl)aminomethyl, N,N-di[C(CH₃)₃]aminomethyl,         N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl,         N-methyl-N—[CH(CH₃)₂]aminomethyl, N-butyl-N-methylaminomethyl,         N-methyl-N-(1-methylpropyl)aminomethyl,         N-methyl-N-(2-methylpropyl)aminomethyl,         N—[C(CH₃)₃]-N-methylaminomethyl, N-ethyl-N-propylaminomethyl,         N-ethyl-N—[CH(CH₃)₂]aminomethyl, N-butyl-N-ethylaminomethyl,         N-ethyl-N-(1-methylpropyl)aminomethyl,         N-ethyl-N-(2-methylpropyl)aminomethyl,         N-ethyl-N—[C(CH₃)₃]aminomethyl,         N—[CH(CH₃)₂]-N-propylaminomethyl, N-butyl-N-propylaminomethyl,         N-(1-methylpropyl)-N-propylaminomethyl,         N-(2-methylpropyl)-N-propylaminomethyl,         N—[C(CH₃)₃]-N-propylaminomethyl,         N-butyl-N-(1-methylethyl)-aminomethyl,         N—(CH(CH₃)₂1-N-(1-methylpropyl)aminomethyl,         N—[CH(CH₃)₂]-N-(2-methylpropyl)aminomethyl,         N—[C(CH₃)₃]-N—[CH(CH₃)₂]aminomethyl,         N-butyl-N-(1-methylpropyl)aminomethyl,         N-butyl-N-(2-methylpropyl)aminomethyl,         N-butyl-N—[C(CH₃)₃]aminomethyl,         N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl,         N—[C(CH₃)₃]-N-(1-methylpropyl)aminomethyl,         N—[C(CH₃)₃]-N-(2-methylpropyl)aminomethyl,         N,N-dimethylaminoethyl, N,N-diethylaminoethyl,         N,N-di(n-propyl)aminoethyl, N,N-di[CH(CH₃)₂]-aminoethyl,         N,N-dibutylaminoethyl, N,N-di(1-methylpropyl)aminoethyl,         N,N-di(2-methylpropyl)aminoethyl, N,N-di[C(CH₃)₃]aminoethyl,         N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl,         N-methyl-N—[CH(CH₃)₂]aminoethyl, N-butyl-N-methylaminoethyl,         N-methyl-N-(1-methylpropyl)aminoethyl,         N-methyl-N-(2-methylpropyl)aminoethyl,         N—[C(CH₃)₃]-N-methylaminoethyl, N-ethyl-N-propylaminoethyl,         N-ethyl-N—[CH(CH₃)₂]aminoethyl, N-butyl-N-ethylaminoethyl,         N-ethyl-N-(1-methylpropyl)aminoethyl,         N-ethyl-N-(2-methylpropyl)aminoethyl,         N-ethyl-N—[C(CH₃)₃]aminoethyl, N—[CH(CH₃)₂]-N-propylaminoethyl,         N-butyl-N-propylaminoethyl,         N-(1-methylpropyl)-N-propylaminoethyl,         N-(2-methylpropyl)-N-propylaminoethyl,         N—[C(CH₃)₃]-N-propylaminoethyl, N-butyl-N—[CH(CH₃)₂]aminoethyl,         N—[CH(CH₃)₂]-N-(1-methylpropyl)aminoethyl,         N—[CH(CH₃)₂]-N-(2-methylpropyl)aminoethyl,         N—[C(CH₃)₃]-N—[CH(CH₃)₂]aminoethyl,         N-butyl-N-(1-methylpropyl)aminoethyl,         N-butyl-N-(2-methylpropyl)aminoethyl,         N-butyl-N—[C(CH₃)₃]aminoethyl,         N-(1-methylpropyl)-N-(2-methylpropyl)aminoethyl,         N—[C(CH₃)₃]-N-(1-methylpropyl)aminoethyl or         N—[C(CH₃)₃]-N-(2-methylpropyl)aminoethyl;     -   aminocarbonyl-C₁-C₄-alkyl: for example CH₂CONH₂, 1-(CONH₂)ethyl,         2-(CONH₂)ethyl, 1-(CONH₂)prop-1-yl, 2-(CONH₂)prop-1-yl,         3-(CONH₂)prop-1-yl, 1-(CONH₂)but-1-yl, 2-(CONH₂)but-1-yl,         3-(CONH₂)but-1-yl, 4-(CONH₂)but-1-yl, 1-(CONH₂)but-2-yl,         2-(CONH₂)but-2-yl, 3-(CONH₂)but-2-yl, 4-(CONH₂)but-2-yl,         1-(CH₂CONH₂)eth-1-yl, 1-(CH₂CONH₂)-1-(CH₃)-eth-1-yl or         1-(CH₂CONH₂)prop-1-yl;     -   (C₁-C₄-alkylamino)carbonyl-C₁-C₄-alkyl: C₁-C₄-alkyl which is         substituted by (C₁-C₄-alkylamino)carbonyl as mentioned above,         i.e., for example, CH₂—CO—NH—CH₃, CH₂—CO—NH—C₂H₅,         CH₂—CO—NH—CH₂—C₂H₅, CH₂—CO—NH—CH(CH₃)₂, CH₂—CO—NH—CH₂CH₂—C₂H₅,         CH₂—CO—NH—CH(CH₃)—C₂H₅, CH₂—CO—NH—CH₂—CH(CH₃)₂,         CH₂—CO—NH—C(CH₃)₃, CH(CH₃)—CO—NH—CH₃, CH(CH₃)—CO—NH—C₂H₅,         2-(CO—NH—CH₃)ethyl, 2-(CO—NH—C₂H₅)ethyl,         2-(CO—NH—CH₂—C₂H₅)ethyl, 2-[CH₂—CO—NH—CH(CH₃)₂]ethyl,         2-(CO—NH—CH₂CH₂—C₂H₅)ethyl, 2-[CO—NH—CH(CH₃)—C₂H₅]ethyl,         2-[CO—NH—CH₂—CH(CH₃)₂]ethyl, 2-[CO—NH—C(CH₃)₃]ethyl,         2-(CO—NH—CH₃)propyl, 2-(CO—NH—C₂H₅)propyl,         2-(CO—NH—CH₂—C₂H₅)propyl, 2-[CH₂—CO—NH—CH(CH₃)₂]propyl,         2-(CO—NH—CH₂CH₂—C₂H₅)propyl, 2-[CO—NH—CH(CH₃)—C₂H₅]propyl,         2-[CO—NH—CH₂—CH(CH₃)₂]propyl, 2-[CO—NH—C(CH₃)₃]propyl,         3-(CO—NR—CH₃)propyl, 3-(CO—NH—C₂H₅)propyl,         3-(CO—NH—CH₂—C₂H₅)propyl, 3-[CH₂—CO—NH—CH(CH₃)₂]propyl,         3-(CO—NH—CH₂CH₂—C₂H₅)propyl, 3-[CO—NH—CH(CH₃)—C₂H₅]propyl,         3-[CO—NH—CH₂—CH(CH₃)₂]Propyl 3-[CO—NH—C(CH₃)₃]propyl,         2-(CO—NH—CH₃)butyl, 2-(CO—NH—C₂H₅)butyl,         2-(CO—NH—CH₂—C₂H₅)butyl, 2-[CH₂—CO—NH—CH(CH₃)₂]butyl,         2-(CO—NH—CH₂CH₂—C₂H₅)butyl, 2-[CO—NH—CH(CH₃)—C₂H₅]butyl,         2-[CO—NH—CH₂—CH(CH₃)₂]butyl, 2-[CO—NH—C(CH₃)₃]butyl,         3-(CO—NH—CH₃)butyl, 3-(CO—NH—C₂H₅)butyl,         3-(CO—NH—CH₂—C₂H₅)butyl, 3-[CH₂—CO—NH—CH(CH₃)₂]butyl,         3-(CO—NH—CH₂CH₂—C₂H₅)butyl, 3-[CO—NH—CH(CH₃)—C₂H₅]butyl,         3-[CO—NH—CH₂—CH(CH₃)₂]butyl, 3-[CO—NH—C(CH₃)₃]butyl,         4-(CO—NH—CH₃)butyl, 4-(CO—NH—C₂H₅)butyl,         4-(CO—NH—CH₂—C₂H₅)butyl, 4-[CH₂—CO—NH—CH(CH₃)₂]butyl,         4-(CO—NH—CH₂CH₂—C₂H₅)butyl, 4-[CO—NH—CH(CH₃)—C₂H₅]butyl,         4-[CO—NH—CH₂—CH(CH₃)₂]butyl or 4-[CO—NH—C(CH₃)₃]butyl,     -   di(C₁-C₄-alkyl)aminocarbonyl-C₁-C₄-alkyl: C₁-C₄-alkyl which is         substituted by di(C₁-C₄-alkyl)aminocarbonyl as mentioned above,         i.e., for example, di(C₁-C₄-alkyl)aminocarbonylmethyl, 1- or         2-di(C₁-C₄-alkyl)aminocarbonylethyl, 1-, 2- or         3-di(C₁-C₄-alkyl)aminocarbonylpropyl;     -   C₁-C₄-alkylphenyl: phenyl which is substituted by C₁-C₄-alkyl as         mentioned above, i.e., for example, 2-tolyl, 3-tolyl, 4-tolyl,         2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-(n-propyl)phenyl,         3-(n-propyl)phenyl, 4-(n-propyl)phenyl, 2-(1-methylethyl)phenyl,         3-(1-methylethyl)phenyl, 4-(1-methylethyl)phenyl,         2-(n-butyl)phenyl, 3-(n-butyl)phenyl, 4-(n-butyl)phenyl,         2-(1-methylpropyl)phenyl, 3-(1-methylpropyl)phenyl,         4-(1-methylpropyl)phenyl, 2-(2-methylpropyl)phenyl,         3-(2-methylpropyl)phenyl, 4-(2-methylpropyl)phenyl,         2-(1,1-dimethylethyl)phenyl, 3-(1,1-dimethylethyl)phenyl,         4-(1,1-dimethylethyl)phenyl;     -   C₃-C₆-alkenyl: a monounsaturated aliphatic hydrocarbon radical         having 3 to 6 carbon atoms which is preferably not attached via         an olefinic carbon atom, for example prop-1-en-1-yl,         prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl,         buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl,         1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl,         penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl,         2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl,         1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl,         3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl,         2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl,         1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl,         1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,         1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl,         hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl,         1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl,         3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl,         1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl,         3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl,         1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl,         3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl,         1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl,         3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,         1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,         1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl,         1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl,         1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,         2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl,         2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl,         3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl,         1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl,         1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl,         2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,         1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,         1-ethyl-2-methylprop-1-en-1-yl or         1-ethyl-2-methylprop-2-en-1-yl;     -   C₃-C₆-alkynyl: an aliphatic hydrocarbon radical which contains a         triple bond and 3 to 6 carbon atoms and which is preferably not         attached via a carbon atom of the triple bond, for example         propargyl (2-propynyl), 1-propynyl, but-1-yn-3-yl,         but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl,         pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl,         3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-3-yl,         hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl,         hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl,         hex-3-yn-2-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl,         3-methylpent-1-yn-5-yl, 4-methylpent-2-yn-4-yl or         4-methylpent-2-yn-5-yl.

With respect to the use of the compounds of the formula I according to the invention as herbicides or as compounds with desiccant/defoliant action, the variables X, R² to R⁶ are preferably as defined below, in each case independently of one another and in particular in combination:

-   X is oxygen, -   R² is hydrogen, fluorine or chlorine, -   R³ is chlorine or cyano, in particular chlorine, -   R⁴, R⁵ independently of one another are hydrogen or C₁-C₄-alkyl, in     particular hydrogen or methyl, -   R⁶ is hydrogen or C₁-C₄-alkyl, in particular hydrogen or methyl.

In a preferred embodiment of the invention, R⁴ or R⁵ is hydrogen and the other radical R⁴ or R⁵ is C₁-C₄-alkyl, in particular methyl or R⁴, R⁵ are each methyl.

Very particular preference is given to compounds of the formula I where

R² is hydrogen, chlorine or fluorine,

R³ is chlorine or cyano,

R⁶ is hydrogen and

X is oxygen.

Particular emphasis is given to the following embodiments of the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I:

-   1. In a particularly preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-A. Hereinbelow, such     compounds are also referred to as compounds I-A. In the compounds     I-A, X and R² to R⁸ preferably and in particular have the meanings     mentioned as being preferred and particularly preferred,     respectively. In particular, in formula II-A,     -   R¹⁰ is C₁-C₄-alkyl or amino, in particular methyl or amino,     -   R¹¹ is C₁-C₄-haloalkyl, in particular trifluoromethyl, and     -   R¹² is hydrogen. -   2. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-B. Hereinbelow, such     compounds are also referred to as compounds I-B. In the compounds     I-B, X and R² to R⁸ preferably and in particular have the meanings     given as being preferred and particularly preferred, respectively.     In particular, in formula. II-B. R¹³, R^(13′) are each independently     of one another C₁-C₄-alkyl, in particular methyl. -   3. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-C. Hereinbelow, such     compounds are also referred to as compounds I-C. In the compounds     I-C, X and R² to R⁸ preferably and in particular have the meanings     given as being preferred and particularly preferred, respectively.     In particular, in formula II-C,     -   R¹⁴ is fluorine or chlorine, in particular chlorine,     -   R¹⁵ is hydrogen or C₁-C₄-alkyl, in particular hydrogen,     -   R¹⁶ is C₁-C₄-haloalkyl, C₁-C₄-alkylsulfonyl or         C₁-C₄-alkylsulfonyloxy, in particular trifluoromethyl,         methylsulfonyl or methylsulfonyloxy. -   4. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-D. Hereinbelow, such     compounds are also referred to as compounds I-D. In the compounds     I-D, X and R² to R⁸ preferably and in particular have the meanings     given as being preferred and particularly preferred, respectively.     In particular, in formula II-D,     -   R¹⁸ is hydrogen, methyl or amino,     -   R¹⁹ is C₁-C₄-haloalkyl or C₁-C₄-alkylsulfonyl, in particular         trifluoromethyl or methylsulfonyl,     -   R²⁰ is hydrogen. -   5. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-E. Hereinbelow, such     compounds are also referred to as compounds I-E. In the compounds     I-E, X and R² to R⁸ preferably and in particular have the meanings     given as being preferred and particularly preferred, respectively.     In particular, in formula II-E,     -   R²¹ is halogen or C₁-C₄-alkyl, in particular chlorine or         bromine,     -   R²² is C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy or C₁-C₄-alkylsulfonyl,         in particular trifluoromethyl, difluoromethyloxy or         methylsulfonyl,     -   R²³ is C₁-C₄-alkyl, in particular methyl. -   6. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-F. Hereinbelow, such     compounds are also referred to as compounds I-F. In the compounds     I-F, X and R² to R⁸ preferably and in particular have those meanings     which have been mentioned as being preferred and particularly     preferred, respectively. In particular in formula II-F,     -   R²⁴ is hydrogen, methyl, difluoromethyl or trifluoromethyl,     -   R²⁵ is methyl or trifluoromethyl,         -   or     -   R²⁴ and R²⁵ together are a chain of the formula —(CH₂)₄—. -   7. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-G. Hereinbelow, such     compounds are also referred to as compounds I-G. In the compounds     I-G, X and R² to R⁸ preferably and in particular have the meanings     given as being preferred and particularly preferred, respectively.     In particular, in formula II-G, A¹, A² are each oxygen. -   8. In a further preferred embodiment, R¹ in formula I is a     heterocyclic radical of the formula II-H. Hereinbelow, such     compounds are also referred to as compounds I-H. In the compounds     I-H, X and R² to R⁸ preferably and in particular have those meanings     which have been mentioned as preferred and particularly preferred,     respectively. In particular, in formula II-H,     -   A³, A⁴ are as defined above and are preferably each oxygen,     -   R²⁶, R²⁷ are each independently of one another C₁-C₄-alkyl or         C₁-C₄-haloalkyl, in particular methyl or difluoromethyl or         trifluoromethyl, or     -   R²⁶ and R²⁷ together are a chain of the formula —CH₂—O—(CH₂)₂—         or —(CH₂)₄—.

Very particular preference is given to the compounds of the formula I, where

R¹ is II-A where R¹⁰=CH₃ or amino, R¹¹=CF₃ and

-   -   R¹²=hydrogen,         R² is hydrogen or fluorine,         R³ is chlorine or cyano,         R⁶ is hydrogen and         X is oxygen.

Very particular preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Aa (≡I where R¹=II-A, R¹⁰=methyl, R¹¹=trifluoromethyl and R¹²=hydrogen, R²=F, R³=Cl, R⁶=H, X=O), where R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Aa.1 to I-Aa.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

TABLE 1 No. R⁴ R⁵ R⁷ R⁸ 1 H H H H 2 H H H CH₃ 3 H H H CH₂CH₃ 4 H H H CH₂CH₂CH₃ 5 H H H CH₂CH₂CH₂CH₃ 6 H H H CH(CH₃)₂ 7 H H H CH₂CH(CH₃)₂ 8 H H H CH(CH₃)CH₂CH₃ 9 H H H C(CH₃)₃ 10 H H H CH₂OCH₃ 11 H H H CH₂CH₂OCH₃ 12 H H H CH₂OCH₂CH₃ 13 H H H CH₂CH₂OCH₂CH₃ 14 H H H CH(CH₃)CH₂OCH₃ 15 H H H CH₂CH₂Cl 16 H H H CH₂CH₂SCH₃ 17 H H H CH₂CH₂S(O)CH₃ 18 H H H CH₂CH₂S(O)₂CH₃ 19 H H H CH₂CH₂CN 20 H H H CH₂CH₂CO₂CH₃ 21 H H H CH₂CH₂CO₂CH₂CH₃ 22 H H H CH₂CH₂NH₂ 23 H H H CH₂CH₂N(CH₃)₂ 24 H H H CH₂CH₂N(CH₂CH₃)₂ 25 H H H CH₂CH═CH₂ 26 H H H C(CH₃)═CH₂ 27 H H H CH₂CH═CHCH₃ 28 H H H C(CH₃)CH═CHCH₃ 29 H H H CH₂C≡CH 30 H H H CH(CH₃)C≡CH 31 H H H CH₂C≡CHCH₃ 32 H H H Ph 33 H H —(CH₂)₄— 34 H H —(CH₂)₅— 35 H H —(CH₂)₂NH(CH₂)₂— 36 H H —(CH₂)₂NCH₃(CH₂)₂— 37 H H —(CH₂)₂O(CH₂)₂— 38 H H —CH₂CH═CHCH₂— 39 H H —CH₂CH═CHCH₂CH₂— 40 H H —CH═CHCH₂CH₂CH₂— 41 H H CH₃ H 42 H H CH₃ CH₃ 43 H H CH₃ CH₂CH₃ 44 H H CH₃ CH₂CH₂CH₃ 45 H H CH₃ CH₂CH₂CH₂CH₃ 46 H H CH₃ CH(CH₃)₂ 47 H H CH₃ CH₂CH(CH₃)₂ 48 H H CH₃ CH(CH₃)CH₂CH₃ 49 H H CH₃ C(CH₃)₃ 50 H H CH₃ CH₂OCH₃ 51 H H CH₃ CH₂CH₂OCH₃ 52 H H CH₃ CH₂OCH₂CH₃ 53 H H CH₃ CH₂CH₂OCH₂CH₃ 54 H H CH₃ CH(CH₃)CH₂OCH₃ 55 H H CH₃ CH₂CH₂Cl 56 H H CH₃ CH₂CH₂SCH₃ 57 H H CH₃ CH₂CH₂S(O)CH₃ 58 H H CH₃ CH₂CH₂S(O)₂CH₃ 59 H H CH₃ CH₂CH₂CN 60 H H CH₃ CH₂CH₂CO₂CH₃ 61 H H CH₃ CH₂CH₂CO₂CH₂CH₃ 62 H H CH₃ CH₂CH₂NH₂ 63 H H CH₃ CH₂CH₂N(CH₃)₂ 64 H H CH₃ CH₂CH₂N(CH₂CH₃)₂ 65 H H CH₃ CH₂CH═CH₂ 66 H H CH₃ C(CH₃)═CH₂ 67 H H CH₃ CH₂CH═CHCH₃ 68 H H CH₃ C(CH₃)CH═CHCH₃ 69 H H CH₃ CH₂C≡CH 70 H H CH₃ CH(CH₃)C≡CH 71 H H CH₃ CH₂C≡CHCH₃ 72 H H CH₃ Ph 73 H H CH₂CH₃ H 74 H H CH₂CH₃ CH₃ 75 H H CH₂CH₃ CH₂CH₃ 76 H H CH₂CH₃ CH₂CH₂CH₃ 77 H H CH₂CH₃ CH₂CH₂CH₂CH₃ 78 H H CH₂CH₃ CH(CH₃)₂ 79 H H CH₂CH₃ CH₂CH(CH₃)₂ 80 H H CH₂CH₃ CH(CH₃)CH₂CH₃ 81 H H CH₂CH₃ C(CH₃)₃ 82 H H CH₂CH₃ CH₂OCH₃ 83 H H CH₂CH₃ CH₂CH₂OCH₃ 84 H H CH₂CH₃ CH₂OCH₂CH₃ 85 H H CH₂CH₃ CH₂CH₂OCH₂CH₃ 86 H H CH₂CH₃ CH(CH₃)CH₂OCH₃ 87 H H CH₂CH₃ CH₂CH₂Cl 88 H H CH₂CH₃ CH₂CH₂SCH₃ 89 H H CH₂CH₃ CH₂CH₂S(O)CH₃ 90 H H CH₂CH₃ CH₂CH₂S(O)₂CH₃ 91 H H CH₂CH₃ CH₂CH₂CN 92 H H CH₂CH₃ CH₂CH₂CO₂CH₃ 93 H H CH₂CH₃ CH₂CH₂CO₂CH₂CH₃ 94 H H CH₂CH₃ CH₂CH₂NH₂ 95 H H CH₂CH₃ CH₂CH₂N(CH₃)₂ 96 H H CH₂CH₃ CH₂CH₂N(CH₂CH₃)₂ 97 H H CH₂CH₃ CH₂CH═CH₂ 98 H H CH₂CH₃ C(CH₃)═CH₂ 99 H H CH₂CH₃ CH₂CH═CHCH₃ 100 H H CH₂CH₃ C(CH₃)CH═CHCH₃ 101 H H CH₂CH₃ CH₂C≡CH 102 H H CH₂CH₃ CH(CH₃)C≡CH 103 H H CH₂CH₃ CH₂C≡CHCH₃ 104 H H CH₂CH₃ Ph 105 H H CH₂CH₂CH₃ H 106 H H CH₂CH₂CH₃ CH₃ 107 H H CH₂CH₂CH₃ CH₂CH₃ 108 H H CH₂CH₂CH₃ CH₂CH₂CH₃ 109 H H CH₂CH₂CH₃ CH₂CH₂CH₂CH₃ 110 H H CH₂CH₂CH₃ CH(CH₃)₂ 111 H H CH₂CH₂CH₃ CH₂CH(CH₃)₂ 112 H H CH₂CH₂CH₃ CH(CH₃)CH₂CH₃ 113 H H CH₂CH₂CH₃ C(CH₃)₃ 114 H H CH₂CH₂CH₃ CH₂OCH₃ 115 H H CH₂CH₂CH₃ CH₂CH₂OCH₃ 116 H H CH₂CH₂CH₃ CH₂OCH₂CH₃ 117 H H CH₂CH₂CH₃ CH₂CH₂OCH₂CH₃ 118 H H CH₂CH₂CH₃ CH(CH₃)CH₂OCH₃ 119 H H CH₂CH₂CH₃ CH₂CH₂Cl 120 H H CH₂CH₂CH₃ CH₂CH₂SCH₃ 121 H H CH₂CH₂CH₃ CH₂CH₂S(O)CH₃ 122 H H CH₂CH₂CH₃ CH₂CH₂S(O)₂CH₃ 123 H H CH₂CH₂CH₃ CH₂CH₂CN 124 H H CH₂CH₂CH₃ CH₂CH₂CO₂CH₃ 125 H H CH₂CH₂CH₃ CH₂CH₂CO₂CH₂CH₃ 126 H H CH₂CH₂CH₃ CH₂CH₂NH₂ 127 H H CH₂CH₂CH₃ CH₂CH₂N(CH₃)₂ 128 H H CH₂CH₂CH₃ CH₂CH₂N(CH₂CH₃)₂ 129 H H CH₂CH₂CH₃ CH₂CH═CH₂ 130 H H CH₂CH₂CH₃ C(CH₃)═CH₂ 131 H H CH₂CH₂CH₃ CH₂CH═CHCH₃ 132 H H CH₂CH₂CH₃ C(CH₃)CH═CHCH₃ 133 H H CH₂CH₂CH₃ CH₂C≡CH 134 H H CH₂CH₂CH₃ CH(CH₃)C≡CH 135 H H CH₂CH₂CH₃ CH₂C≡CHCH₃ 136 H H CH₂CH₂CH₃ Ph 137 H H CH(CH₃)₂ H 138 H H CH(CH₃)₂ CH₃ 139 H H CH(CH₃)₂ CH₂CH₃ 140 H H CH(CH₃)₂ CH₂CH₂CH₃ 141 H H CH(CH₃)₂ CH₂CH₂CH₂CH₃ 142 H H CH(CH₃)₂ CH(CH₃)₂ 143 H H CH(CH₃)₂ CH₂CH(CH₃)₂ 144 H H CH(CH₃)₂ CH(CH₃)CH₂CH₃ 145 H H CH(CH₃)₂ C(CH₃)₃ 146 H H CH(CH₃)₂ CH₂OCH₃ 147 H H CH(CH₃)₂ CH₂CH₂OCH₃ 148 H H CH(CH₃)₂ CH₂OCH₂CH₃ 149 H H CH(CH₃)₂ CH₂CH₂OCH₂CH₃ 150 H H CH(CH₃)₂ CH(CH₃)CH₂OCH₃ 151 H H CH(CH₃)₂ CH₂CH₂Cl 152 H H CH(CH₃)₂ CH₂CH₂SCH₃ 153 H H CH(CH₃)₂ CH₂CH₂S(O)CH₃ 154 H H CH(CH₃)₂ CH₂CH₂S(O)₂CH₃ 155 H H CH(CH₃)₂ CH₂CH₂CN 156 H H CH(CH₃)₂ CH₂CH₂CO₂CH₃ 157 H H CH(CH₃)₂ CH₂CH₂CO₂CH₂CH₃ 158 H H CH(CH₃)₂ CH₂CH₂NH₂ 159 H H CH(CH₃)₂ CH₂CH₂N(CH₃)₂ 160 H H CH(CH₃)₂ CH₂CH₂N(CH₂CH₃)₂ 161 H H CH(CH₃)₂ CH₂CH═CH₂ 162 H H CH(CH₃)₂ C(CH₃)═CH₂ 163 H H CH(CH₃)₂ CH₂CH═CHCH₃ 164 H H CH(CH₃)₂ C(CH₃)CH═CHCH₃ 165 H H CH(CH₃)₂ CH₂C≡CH 166 H H CH(CH₃)₂ CH(CH₃)C≡CH 167 H H CH(CH₃)₂ CH₂C≡CHCH₃ 168 H H CH(CH₃)₂ Ph 169 H H CH₂CH═CH₂ H 170 H H CH₂CH═CH₂ CH₃ 171 H H CH₂CH═CH₂ CH₂CH₃ 172 H H CH₂CH═CH₂ CH₂CH₂CH₃ 173 H H CH₂CH═CH₂ CH₂CH₂CH₂CH₃ 174 H H CH₂CH═CH₂ CH(CH₃)₂ 175 H H CH₂CH═CH₂ CH₂CH(CH₃)₂ 176 H H CH₂CH═CH₂ CH(CH₃)CH₂CH₃ 177 H H CH₂CH═CH₂ C(CH₃)₃ 178 H H CH₂CH═CH₂ CH₂OCH₃ 179 H H CH₂CH═CH₂ CH₂CH₂OCH₃ 180 H H CH₂CH═CH₂ CH₂OCH₂CH₃ 181 H H CH₂CH═CH₂ CH₂CH₂OCH₂CH₃ 182 H H CH₂CH═CH₂ CH(CH₃)CH₂OCH₃ 183 H H CH₂CH═CH₂ CH₂CH₂Cl 184 H H CH₂CH═CH₂ CH₂CH₂SCH₃ 185 H H CH₂CH═CH₂ CH₂CH₂S(O)CH₃ 186 H H CH₂CH═CH₂ CH₂CH₂S(O)₂CH₃ 187 H H CH₂CH═CH₂ CH₂CH₂CN 188 H H CH₂CH═CH₂ CH₂CH₂CO₂CH₃ 189 H H CH₂CH═CH₂ CH₂CH₂CO₂CH₂CH₃ 190 H H CH₂CH═CH₂ CH₂CH₂NH₂ 191 H H CH₂CH═CH₂ CH₂CH₂N(CH₃)₂ 192 H H CH₂CH═CH₂ CH₂CH₂N(CH₂CH₃)₂ 193 H H CH₂CH═CH₂ CH₂CH═CH₂ 194 H H CH₂CH═CH₂ C(CH₃)═CH₂ 195 H H CH₂CH═CH₂ CH₂CH═CHCH₃ 196 H H CH₂CH═CH₂ C(CH₃)CH═CHCH₃ 197 H H CH₂CH═CH₂ CH₂C≡CH 198 H H CH₂CH═CH₂ CH(CH₃)C≡CH 199 H H CH₂CH═CH₂ CH₂C≡CHCH₃ 200 H H CH₂CH═CH₂ Ph 201 CH₃ H H H 202 CH₃ H H CH₃ 203 CH₃ H H CH₂CH₃ 204 CH₃ H H CH₂CH₂CH₃ 205 CH₃ H H CH₂CH₂CH₂CH₃ 206 CH₃ H H CH(CH₃)₂ 207 CH₃ H H CH₂CH(CH₃)₂ 208 CH₃ H H CH(CH₃)CH₂CH₃ 209 CH₃ H H C(CH₃)₃ 210 CH₃ H H CH₂OCH₃ 211 CH₃ H H CH₂CH₂OCH₃ 212 CH₃ H H CH₂OCH₂CH₃ 213 CH₃ H H CH₂CH₂OCH₂CH₃ 214 CH₃ H H CH(CH₃)CH₂OCH₃ 215 CH₃ H H CH₂CH₂Cl 216 CH₃ H H CH₂CH₂SCH₃ 217 CH₃ H H CH₂CH₂S(O)CH₃ 218 CH₃ H H CH₂CH₂S(O)₂CH₃ 219 CH₃ H H CH₂CH₂CN 220 CH₃ H H CH₂CH₂CO₂CH₃ 221 CH₃ H H CH₂CH₂CO₂CH₂CH₃ 222 CH₃ H H CH₂CH₂NH₂ 223 CH₃ H H CH₂CH₂N(CH₃)₂ 224 CH₃ H H CH₂CH₂N(CH₂CH₃)₂ 225 CH₃ H H CH₂CH═CH₂ 226 CH₃ H H C(CH₃)═CH₂ 227 CH₃ H H CH₂CH═CHCH₃ 228 CH₃ H H C(CH₃)CH═CHCH₃ 229 CH₃ H H CH₂C≡CH 230 CH₃ H H CH(CH₃)C≡CH 231 CH₃ H H CH₂C≡CHCH₃ 232 CH₃ H H Ph 233 CH₃ H —(CH₂)₄— 234 CH₃ H —(CH₂)₅— 235 CH₃ H —(CH₂)₂NH(CH₂)₂— 236 CH₃ H —(CH₂)₂NCH₃(CH₂)₂— 237 CH₃ H —(CH₂)₂O(CH₂)₂— 238 CH₃ H —CH₂CH═CHCH₂— 239 CH₃ H —CH₂CH═CHCH₂CH₂— 240 CH₃ H —CH═CHCH₂CH₂CH₂— 241 CH₃ H CH₃ H 242 CH₃ H CH₃ CH₃ 243 CH₃ H CH₃ CH₂CH₃ 244 CH₃ H CH₃ CH₂CH₂CH₃ 245 CH₃ H CH₃ CH₂CH₂CH₂CH₃ 246 CH₃ H CH₃ CH(CH₃)₂ 247 CH₃ H CH₃ CH₂CH(CH₃)₂ 248 CH₃ H CH₃ CH(CH₃)CH₂CH₃ 249 CH₃ H CH₃ C(CH₃)₃ 250 CH₃ H CH₃ CH₂OCH₃ 251 CH₃ H CH₃ CH₂CH₂OCH₃ 252 CH₃ H CH₃ CH₂OCH₂CH₃ 253 CH₃ H CH₃ CH₂CH₂OCH₂CH₃ 254 CH₃ H CH₃ CH(CH₃)CH₂OCH₃ 255 CH₃ H CH₃ CH₂CH₂Cl 256 CH₃ H CH₃ CH₂CH₂SCH₃ 257 CH₃ H CH₃ CH₂CH₂S(O)CH₃ 258 CH₃ H CH₃ CH₂CH₂S(O)₂CH₃ 259 CH₃ H CH₃ CH₂CH₂CN 260 CH₃ H CH₃ CH₂CH₂CO₂CH₃ 261 CH₃ H CH₃ CH₂CH₂CO₂CH₂CH₃ 262 CH₃ H CH₃ CH₂CH₂NH₂ 263 CH₃ H CH₃ CH₂CH₂N(CH₃)₂ 264 CH₃ H CH₃ CH₂CH₂N(CH₂CH₃)₂ 265 CH₃ H CH₃ CH₂CH═CH₂ 266 CH₃ H CH₃ C(CH₃)═CH₂ 267 CH₃ H CH₃ CH₂CH═CHCH₃ 268 CH₃ H CH₃ C(CH₃)CH═CHCH₃ 269 CH₃ H CH₃ CH₂C≡CH 270 CH₃ H CH₃ CH(CH₃)C≡CH 271 CH₃ H CH₃ CH₂C≡CHCH₃ 272 CH₃ H CH₃ Ph 273 CH₃ H CH₂CH₃ H 274 CH₃ H CH₂CH₃ CH₃ 275 CH₃ H CH₂CH₃ CH₂CH₃ 276 CH₃ H CH₂CH₃ CH₂CH₂CH₃ 277 CH₃ H CH₂CH₃ CH₂CH₂CH₂CH₃ 278 CH₃ H CH₂CH₃ CH(CH₃)₂ 279 CH₃ H CH₂CH₃ CH₂CH(CH₃)₂ 280 CH₃ H CH₂CH₃ CH(CH₃)CH₂CH₃ 281 CH₃ H CH₂CH₃ C(CH₃)₃ 282 CH₃ H CH₂CH₃ CH₂OCH₃ 283 CH₃ H CH₂CH₃ CH₂CH₂OCH₃ 284 CH₃ H CH₂CH₃ CH₂OCH₂CH₃ 285 CH₃ H CH₂CH₃ CH₂CH₂OCH₂CH₃ 286 CH₃ H CH₂CH₃ CH(CH₃)CH₂OCH₃ 287 CH₃ H CH₂CH₃ CH₂CH₂Cl 288 CH₃ H CH₂CH₃ CH₂CH₂SCH₃ 289 CH₃ H CH₂CH₃ CH₂CH₂S(O)CH₃ 290 CH₃ H CH₂CH₃ CH₂CH₂S(O)₂CH₃ 291 CH₃ H CH₂CH₃ CH₂CH₂CN 292 CH₃ H CH₂CH₃ CH₂CH₂CO₂CH₃ 293 CH₃ H CH₂CH₃ CH₂CH₂CO₂CH₂CH₃ 294 CH₃ H CH₂CH₃ CH₂CH₂NH₂ 295 CH₃ H CH₂CH₃ CH₂CH₂N(CH₃)₂ 296 CH₃ H CH₂CH₃ CH₂CH₂N(CH₂CH₃)₂ 297 CH₃ H CH₂CH₃ CH₂CH═CH₂ 298 CH₃ H CH₂CH₃ C(CH₃)═CH₂ 299 CH₃ H CH₂CH₃ CH₂CH═CHCH₃ 300 CH₃ H CH₂CH₃ C(CH₃)CH═CHCH₃ 301 CH₃ H CH₂CH₃ CH₂C≡CH 302 CH₃ H CH₂CH₃ CH(CH₃)C≡CH 303 CH₃ H CH₂CH₃ CH₂C≡CHCH₃ 304 CH₃ H CH₂CH₃ Ph 305 CH₃ H CH₂CH₂CH₃ H 306 CH₃ H CH₂CH₂CH₃ CH₃ 307 CH₃ H CH₂CH₂CH₃ CH₂CH₃ 308 CH₃ H CH₂CH₂CH₃ CH₂CH₂CH₃ 309 CH₃ H CH₂CH₂CH₃ CH₂CH₂CH₂CH₃ 310 CH₃ H CH₂CH₂CH₃ CH(CH₃)₂ 311 CH₃ H CH₂CH₂CH₃ CH₂CH(CH₃)₂ 312 CH₃ H CH₂CH₂CH₃ CH(CH₃)CH₂CH₃ 313 CH₃ H CH₂CH₂CH₃ C(CH₃)₃ 314 CH₃ H CH₂CH₂CH₃ CH₂OCH₃ 315 CH₃ H CH₂CH₂CH₃ CH₂CH₂OCH₃ 316 CH₃ H CH₂CH₂CH₃ CH₂OCH₂CH₃ 317 CH₃ H CH₂CH₂CH₃ CH₂CH₂OCH₂CH₃ 318 CH₃ H CH₂CH₂CH₃ CH(CH₃)CH₂OCH₃ 319 CH₃ H CH₂CH₂CH₃ CH₂CH₂Cl 320 CH₃ H CH₂CH₂CH₃ CH₂CH₂SCH₃ 321 CH₃ H CH₂CH₂CH₃ CH₂CH₂S(O)CH₃ 322 CH₃ H CH₂CH₂CH₃ CH₂CH₂S(O)₂CH₃ 323 CH₃ H CH₂CH₂CH₃ CH₂CH₂CN 324 CH₃ H CH₂CH₂CH₃ CH₂CH₂CO₂CH₃ 325 CH₃ H CH₂CH₂CH₃ CH₂CH₂CO₂CH₂CH₃ 326 CH₃ H CH₂CH₂CH₃ CH₂CH₂NH₂ 327 CH₃ H CH₂CH₂CH₃ CH₂CH₂N(CH₃)₂ 328 CH₃ H CH₂CH₂CH₃ CH₂CH₂N(CH₂CH₃)₂ 329 CH₃ H CH₂CH₂CH₃ CH₂CH═CH₂ 330 CH₃ H CH₂CH₂CH₃ C(CH₃)═CH₂ 331 CH₃ H CH₂CH₂CH₃ CH₂CH═CHCH₃ 332 CH₃ H CH₂CH₂CH₃ C(CH₃)CH═CHCH₃ 333 CH₃ H CH₂CH₂CH₃ CH₂C≡CH 334 CH₃ H CH₂CH₂CH₃ CH(CH₃)C≡CH 335 CH₃ H CH₂CH₂CH₃ CH₂C≡CHCH₃ 336 CH₃ H CH₂CH₂CH₃ Ph 337 CH₃ H CH(CH₃)₂ H 338 CH₃ H CH(CH₃)₂ CH₃ 339 CH₃ H CH(CH₃)₂ CH₂CH₃ 340 CH₃ H CH(CH₃)₂ CH₂CH₂CH₃ 341 CH₃ H CH(CH₃)₂ CH₂CH₂CH₂CH₃ 342 CH₃ H CH(CH₃)₂ CH(CH₃)₂ 343 CH₃ H CH(CH₃)₂ CH₂CH(CH₃)₂ 344 CH₃ H CH(CH₃)₂ CH(CH₃)CH₂CH₃ 345 CH₃ H CH(CH₃)₂ C(CH₃)₃ 346 CH₃ H CH(CH₃)₂ CH₂OCH₃ 347 CH₃ H CH(CH₃)₂ CH₂CH₂OCH₃ 348 CH₃ H CH(CH₃)₂ CH₂OCH₂CH₃ 349 CH₃ H CH(CH₃)₂ CH₂CH₂OCH₂CH₃ 350 CH₃ H CH(CH₃)₂ CH(CH₃)CH₂OCH₃ 351 CH₃ H CH(CH₃)₂ CH₂CH₂Cl 352 CH₃ H CH(CH₃)₂ CH₂CH₂SCH₃ 353 CH₃ H CH(CH₃)₂ CH₂CH₂S(O)CH₃ 354 CH₃ H CH(CH₃)₂ CH₂CH₂S(O)₂CH₃ 355 CH₃ H CH(CH₃)₂ CH₂CH₂CN 356 CH₃ H CH(CH₃)₂ CH₂CH₂CO₂CH₃ 357 CH₃ H CH(CH₃)₂ CH₂CH₂CO₂CH₂CH₃ 358 CH₃ H CH(CH₃)₂ CH₂CH₂NH₂ 359 CH₃ H CH(CH₃)₂ CH₂CH₂N(CH₃)₂ 360 CH₃ H CH(CH₃)₂ CH₂CH₂N(CH₂CH₃)₂ 361 CH₃ H CH(CH₃)₂ CH₂CH═CH₂ 362 CH₃ H CH(CH₃)₂ C(CH₃)═CH₂ 363 CH₃ H CH(CH₃)₂ CH₂CH═CHCH₃ 364 CH₃ H CH(CH₃)₂ C(CH₃)CH═CHCH₃ 365 CH₃ H CH(CH₃)₂ CH₂C≡CH 366 CH₃ H CH(CH₃)₂ CH(CH₃)C≡CH 367 CH₃ H CH(CH₃)₂ CH₂C≡CHCH₃ 368 CH₃ H CH(CH₃)₂ Ph 369 CH₃ H CH₂CH═CH₂ H 370 CH₃ H CH₂CH═CH₂ CH₃ 371 CH₃ H CH₂CH═CH₂ CH₂CH₃ 372 CH₃ H CH₂CH═CH₂ CH₂CH₂CH₃ 373 CH₃ H CH₂CH═CH₂ CH₂CH₂CH₂CH₃ 374 CH₃ H CH₂CH═CH₂ CH(CH₃)₂ 375 CH₃ H CH₂CH═CH₂ CH₂CH(CH₃)₂ 376 CH₃ H CH₂CH═CH₂ CH(CH₃)CH₂CH₃ 377 CH₃ H CH₂CH═CH₂ C(CH₃)₃ 378 CH₃ H CH₂CH═CH₂ CH₂OCH₃ 379 CH₃ H CH₂CH═CH₂ CH₂CH₂OCH₃ 380 CH₃ H CH₂CH═CH₂ CH₂OCH₂CH₃ 381 CH₃ H CH₂CH═CH₂ CH₂CH₂OCH₂CH₃ 382 CH₃ H CH₂CH═CH₂ CH(CH₃)CH₂OCH₃ 383 CH₃ H CH₂CH═CH₂ CH₂CH₂Cl 384 CH₃ H CH₂CH═CH₂ CH₂CH₂SCH₃ 385 CH₃ H CH₂CH═CH₂ CH₂CH₂S(O)CH₃ 386 CH₃ H CH₂CH═CH₂ CH₂CH₂S(O)₂CH₃ 387 CH₃ H CH₂CH═CH₂ CH₂CH₂CN 388 CH₃ H CH₂CH═CH₂ CH₂CH₂CO₂CH₃ 389 CH₃ H CH₂CH═CH₂ CH₂CH₂CO₂CH₂CH₃ 390 CH₃ H CH₂CH═CH₂ CH₂CH₂NH₂ 391 CH₃ H CH₂CH═CH₂ CH₂CH₂N(CH₃)₂ 392 CH₃ H CH₂CH═CH₂ CH₂CH₂N(CH₂CH₃)₂ 393 CH₃ H CH₂CH═CH₂ CH₂CH═CH₂ 394 CH₃ H CH₂CH═CH₂ C(CH₃)═CH₂ 395 CH₃ H CH₂CH═CH₂ CH₂CH═CHCH₃ 396 CH₃ H CH₂CH═CH₂ C(CH₃)CH═CHCH₃ 397 CH₃ H CH₂CH═CH₂ CH₂C≡CH 398 CH₃ H CH₂CH═CH₂ CH(CH₃)C≡CH 399 CH₃ H CH₂CH═CH₂ CH₂C≡CHCH₃ 400 CH₃ H CH₂CH═CH₂ Ph 401 CH₃ CH₃ H H 402 CH₃ CH₃ H CH₃ 403 CH₃ CH₃ H CH₂CH₃ 404 CH₃ CH₃ H CH₂CH₂CH₃ 405 CH₃ CH₃ H CH₂CH₂CH₂CH₃ 406 CH₃ CH₃ H CH(CH₃)₂ 407 CH₃ CH₃ H CH₂CH(CH₃)₂ 408 CH₃ CH₃ H CH(CH₃)CH₂CH₃ 409 CH₃ CH₃ H C(CH₃)₃ 410 CH₃ CH₃ H CH₂OCH₃ 411 CH₃ CH₃ H CH₂CH₂OCH₃ 412 CH₃ CH₃ H CH₂OCH₂CH₃ 413 CH₃ CH₃ H CH₂CH₂OCH₂CH₃ 414 CH₃ CH₃ H CH(CH₃)CH₂OCH₃ 415 CH₃ CH₃ H CH₂CH₂Cl 416 CH₃ CH₃ H CH₂CH₂SCH₃ 417 CH₃ CH₃ H CH₂CH₂S(O)CH₃ 418 CH₃ CH₃ H CH₂CH₂S(O)₂CH₃ 419 CH₃ CH₃ H CH₂CH₂CN 420 CH₃ CH₃ H CH₂CH₂CO₂CH₃ 421 CH₃ CH₃ H CH₂CH₂CO₂CH₂CH₃ 422 CH₃ CH₃ H CH₂CH₂NH₂ 423 CH₃ CH₃ H CH₂CH₂N(CH₃)₂ 424 CH₃ CH₃ H CH₂CH₂N(CH₂CH₃)₂ 425 CH₃ CH₃ H CH₂CH═CH₂ 426 CH₃ CH₃ H C(CH₃)═CH₂ 427 CH₃ CH₃ H CH₂CH═CHCH₃ 428 CH₃ CH₃ H C(CH₃)CH═CHCH₃ 429 CH₃ CH₃ H CH₂C≡CH 430 CH₃ CH₃ H CH(CH₃)C≡CH 431 CH₃ CH₃ H CH₂C≡CHCH₃ 432 CH₃ CH₃ H Ph 433 CH₃ CH₃ —(CH₂)₄— 434 CH₃ CH₃ —(CH₂)₅— 435 CH₃ CH₃ —(CH₂)₂NH(CH₂)₂— 436 CH₃ CH₃ —(CH₂)₂NCH₃(CH₂)₂— 437 CH₃ CH₃ —(CH₂)₂O(CH₂)₂— 438 CH₃ CH₃ —CH₂CH═CHCH₂— 439 CH₃ CH₃ —CH₂CH═CHCH₂CH₂— 440 CH₃ CH₃ —CH═CHCH₂CH₂CH₂— 441 CH₃ CH₃ CH₃ H 442 CH₃ CH₃ CH₃ CH₃ 443 CH₃ CH₃ CH₃ CH₂CH₃ 444 CH₃ CH₃ CH₃ CH₂CH₂CH₃ 445 CH₃ CH₃ CH₃ CH₂CH₂CH₂CH₃ 446 CH₃ CH₃ CH₃ CH(CH₃)₂ 447 CH₃ CH₃ CH₃ CH₂CH(CH₃)₂ 448 CH₃ CH₃ CH₃ CH(CH₃)CH₂CH₃ 449 CH₃ CH₃ CH₃ C(CH₃)₃ 450 CH₃ CH₃ CH₃ CH₂OCH₃ 451 CH₃ CH₃ CH₃ CH₂CH₂OCH₃ 452 CH₃ CH₃ CH₃ CH₂OCH₂CH₃ 453 CH₃ CH₃ CH₃ CH₂CH₂OCH₂CH₃ 454 CH₃ CH₃ CH₃ CH(CH₃)CH₂OCH₃ 455 CH₃ CH₃ CH₃ CH₂CH₂Cl 456 CH₃ CH₃ CH₃ CH₂CH₂SCH₃ 457 CH₃ CH₃ CH₃ CH₂CH₂S(O)CH₃ 458 CH₃ CH₃ CH₃ CH₂CH₂S(O)₂CH₃ 459 CH₃ CH₃ CH₃ CH₂CH₂CN 460 CH₃ CH₃ CH₃ CH₂CH₂CO₂CH₃ 461 CH₃ CH₃ CH₃ CH₂CH₂CO₂CH₂CH₃ 462 CH₃ CH₃ CH₃ CH₂CH₂NH₂ 463 CH₃ CH₃ CH₃ CH₂CH₂N(CH₃)₂ 464 CH₃ CH₃ CH₃ CH₂CH₂N(CH₂CH₃)₂ 465 CH₃ CH₃ CH₃ CH₂CH═CH₂ 466 CH₃ CH₃ CH₃ C(CH₃)═CH₂ 467 CH₃ CH₃ CH₃ CH₂CH═CHCH₃ 468 CH₃ CH₃ CH₃ C(CH₃)CH═CHCH₃ 469 CH₃ CH₃ CH₃ CH₂C≡CH 470 CH₃ CH₃ CH₃ CH(CH₃)C≡CH 471 CH₃ CH₃ CH₃ CH₂C≡CHCH₃ 472 CH₃ CH₃ CH₃ Ph 473 CH₃ CH₃ CH₂CH₃ H 474 CH₃ CH₃ CH₂CH₃ CH₃ 475 CH₃ CH₃ CH₂CH₃ CH₂CH₃ 476 CH₃ CH₃ CH₂CH₃ CH₂CH₂CH₃ 477 CH₃ CH₃ CH₂CH₃ CH₂CH₂CH₂CH₃ 478 CH₃ CH₃ CH₂CH₃ CH(CH₃)₂ 479 CH₃ CH₃ CH₂CH₃ CH₂CH(CH₃)₂ 480 CH₃ CH₃ CH₂CH₃ CH(CH₃)CH₂CH₃ 481 CH₃ CH₃ CH₂CH₃ C(CH₃)₃ 482 CH₃ CH₃ CH₂CH₃ CH₂OCH₃ 483 CH₃ CH₃ CH₂CH₃ CH₂CH₂OCH₃ 484 CH₃ CH₃ CH₂CH₃ CH₂OCH₂CH₃ 485 CH₃ CH₃ CH₂CH₃ CH₂CH₂OCH₂CH₃ 486 CH₃ CH₃ CH₂CH₃ CH(CH₃)CH₂OCH₃ 487 CH₃ CH₃ CH₂CH₃ CH₂CH₂Cl 488 CH₃ CH₃ CH₂CH₃ CH₂CH₂SCH₃ 489 CH₃ CH₃ CH₂CH₃ CH₂CH₂S(O)CH₃ 490 CH₃ CH₃ CH₂CH₃ CH₂CH₂S(O)₂CH₃ 491 CH₃ CH₃ CH₂CH₃ CH₂CH₂CN 492 CH₃ CH₃ CH₂CH₃ CH₂CH₂CO₂CH₃ 493 CH₃ CH₃ CH₂CH₃ CH₂CH₂CO₂CH₂CH₃ 494 CH₃ CH₃ CH₂CH₃ CH₂CH₂NH₂ 495 CH₃ CH₃ CH₂CH₃ CH₂CH₂N(CH₃)₂ 496 CH₃ CH₃ CH₂CH₃ CH₂CH₂N(CH₂CH₃)₂ 497 CH₃ CH₃ CH₂CH₃ CH₂CH═CH₂ 498 CH₃ CH₃ CH₂CH₃ C(CH₃)═CH₂ 499 CH₃ CH₃ CH₂CH₃ CH₂CH═CHCH₃ 500 CH₃ CH₃ CH₂CH₃ C(CH₃)CH═CHCH₃ 501 CH₃ CH₃ CH₂CH₃ CH₂C≡CH 502 CH₃ CH₃ CH₂CH₃ CH(CH₃)C≡CH 503 CH₃ CH₃ CH₂CH₃ CH₂C≡CHCH₃ 504 CH₃ CH₃ CH₂CH₃ Ph 505 CH₃ CH₃ CH₂CH₂CH₃ H 506 CH₃ CH₃ CH₂CH₂CH₃ CH₃ 507 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₃ 508 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂CH₃ 509 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂CH₂CH₃ 510 CH₃ CH₃ CH₂CH₂CH₃ CH(CH₃)₂ 511 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH(CH₃)₂ 512 CH₃ CH₃ CH₂CH₂CH₃ CH(CH₃)CH₂CH₃ 513 CH₃ CH₃ CH₂CH₂CH₃ C(CH₃)₃ 514 CH₃ CH₃ CH₂CH₂CH₃ CH₂OCH₃ 515 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂OCH₃ 516 CH₃ CH₃ CH₂CH₂CH₃ CH₂OCH₂CH₃ 517 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂OCH₂CH₃ 518 CH₃ CH₃ CH₂CH₂CH₃ CH(CH₃)CH₂OCH₃ 519 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂Cl 520 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂SCH₃ 521 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂S(O)CH₃ 522 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂S(O)₂CH₃ 523 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂CN 524 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂CO₂CH₃ 525 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂CO₂CH₂CH₃ 526 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂NH₂ 527 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂N(CH₃)₂ 528 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH₂N(CH₂CH₃)₂ 529 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH═CH₂ 530 CH₃ CH₃ CH₂CH₂CH₃ C(CH₃)═CH₂ 531 CH₃ CH₃ CH₂CH₂CH₃ CH₂CH═CHCH₃ 532 CH₃ CH₃ CH₂CH₂CH₃ C(CH₃)CH═CHCH₃ 533 CH₃ CH₃ CH₂CH₂CH₃ CH₂C≡CH 534 CH₃ CH₃ CH₂CH₂CH₃ CH(CH₃)C≡CH 535 CH₃ CH₃ CH₂CH₂CH₃ CH₂C≡CHCH₃ 536 CH₃ CH₃ CH₂CH₂CH₃ Ph 537 CH₃ CH₃ CH(CH₃)₂ H 538 CH₃ CH₃ CH(CH₃)₂ CH₃ 539 CH₃ CH₃ CH(CH₃)₂ CH₂CH₃ 540 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂CH₃ 541 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂CH₂CH₃ 542 CH₃ CH₃ CH(CH₃)₂ CH(CH₃)₂ 543 CH₃ CH₃ CH(CH₃)₂ CH₂CH(CH₃)₂ 544 CH₃ CH₃ CH(CH₃)₂ CH(CH₃)CH₂CH₃ 545 CH₃ CH₃ CH(CH₃)₂ C(CH₃)₃ 546 CH₃ CH₃ CH(CH₃)₂ CH₂OCH₃ 547 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂OCH₃ 548 CH₃ CH₃ CH(CH₃)₂ CH₂OCH₂CH₃ 549 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂OCH₂CH₃ 550 CH₃ CH₃ CH(CH₃)₂ CH(CH₃)CH₂OCH₃ 551 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂Cl 552 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂SCH₃ 553 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂S(O)CH₃ 554 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂S(O)₂CH₃ 555 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂CN 556 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂CO₂CH₃ 557 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂CO₂CH₂CH₃ 558 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂NH₂ 559 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂N(CH₃)₂ 560 CH₃ CH₃ CH(CH₃)₂ CH₂CH₂N(CH₂CH₃)₂ 561 CH₃ CH₃ CH(CH₃)₂ CH₂CH═CH₂ 562 CH₃ CH₃ CH(CH₃)₂ C(CH₃)═CH₂ 563 CH₃ CH₃ CH(CH₃)₂ CH₂CH═CHCH₃ 564 CH₃ CH₃ CH(CH₃)₂ C(CH₃)CH═CHCH₃ 565 CH₃ CH₃ CH(CH₃)₂ CH₂C≡CH 566 CH₃ CH₃ CH(CH₃)₂ CH(CH₃)C≡CH 567 CH₃ CH₃ CH(CH₃)₂ CH₂C≡CHCH₃ 568 CH₃ CH₃ CH(CH₃)₂ Ph 569 CH₃ CH₃ CH₂CH═CH₂ H 570 CH₃ CH₃ CH₂CH═CH₂ CH₃ 571 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₃ 572 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂CH₃ 573 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂CH₂CH₃ 574 CH₃ CH₃ CH₂CH═CH₂ CH(CH₃)₂ 575 CH₃ CH₃ CH₂CH═CH₂ CH₂CH(CH₃)₂ 576 CH₃ CH₃ CH₂CH═CH₂ CH(CH₃)CH₂CH₃ 577 CH₃ CH₃ CH₂CH═CH₂ C(CH₃)₃ 578 CH₃ CH₃ CH₂CH═CH₂ CH₂OCH₃ 579 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂OCH₃ 580 CH₃ CH₃ CH₂CH═CH₂ CH₂OCH₂CH₃ 581 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂OCH₂CH₃ 582 CH₃ CH₃ CH₂CH═CH₂ CH(CH₃)CH₂OCH₃ 583 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂Cl 584 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂SCH₃ 585 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂S(O)CH₃ 586 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂S(O)₂CH₃ 587 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂CN 588 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂CO₂CH₃ 589 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂CO₂CH₂CH₃ 590 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂NH₂ 591 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂N(CH₃)₂ 592 CH₃ CH₃ CH₂CH═CH₂ CH₂CH₂N(CH₂CH₃)₂ 593 CH₃ CH₃ CH₂CH═CH₂ CH₂CH═CH₂ 594 CH₃ CH₃ CH₂CH═CH₂ C(CH₃)═CH₂ 595 CH₃ CH₃ CH₂CH═CH₂ CH₂CH═CHCH₃ 596 CH₃ CH₃ CH₂CH═CH₂ C(CH₃)CH═CHCH₃ 597 CH₃ CH₃ CH₂CH═CH₂ CH₂C≡CH 598 CH₃ CH₃ CH₂CH═CH₂ CH(CH₃)C≡CH 599 CH₃ CH₃ CH₂CH═CH₂ CH₂C≡CHCH₃ 600 CH₃ CH₃ CH₂CH═CH₂ Ph

Very particular preference is also given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ab (≡I where R¹=II-A, R¹⁰=methyl, R¹¹=trifluoromethyl and R¹²=hydrogen, R²=H, R³=Cl, R⁶=H, X=O), where R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ab.1 to I-Ab.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Very particular preference is also given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ac (≡I where R¹=II-A, R¹⁰=amino, R¹¹=trifluoromethyl and R¹²=hydrogen, R²=F, R³=Cl, R⁶=H, X=O), where R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ac.1 to I-Ac.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Very particular preference is also given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ad (≡I where R¹=II-A, R¹⁰=amino, R¹¹=trifluoromethyl and R¹²=hydrogen, R²=H, R³=Cl, R⁶=H, X=O), where R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ad.1 to I-Ad.600, in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-B preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ba (≡I where R¹=II-B, R^(13′), R¹³ are each methyl, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ba.1 to I-Ba.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-B preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Bb (≡I where R¹=II-B, R^(13′), R¹³ are each methyl, R²=H, R³=Cl; R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Bb.1 to I-Bb.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-C preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ca (≡I where R¹=II-C, R¹⁴=chlorine, R¹⁵, R¹⁷=hydrogen, R¹⁶=trifluoromethyl, R²=F; R³=Cl; R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ca.1 to I-Ca.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-C preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Cb (≡I where R¹=II-C, R¹⁴=chlorine, R¹⁵, R¹⁷=hydrogen, R¹⁶=trifluoromethyl, R²=H; R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Cb.1 to I-Cb.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-C preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Cc (≡I where R¹=II-C, R¹⁴=chlorine, R¹⁵, R¹⁷=hydrogen, R¹⁶=methylsulfonyl, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Cc.1 to I-Cc.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-C preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Cd (≡I where R¹=II-C, R¹⁴=chlorine, R¹⁵, R¹⁷=hydrogen, R¹⁶=methylsulfonyl; R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Cd.1 to I-Cd.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-C preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ce (≡I where R¹=II-C, R¹⁴=chlorine, R¹⁵, R¹⁷=hydrogen, R¹⁶=methylsulfonyloxy, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ce.1 to I-Ce.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-C preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Cf (≡I where R¹=II-C, R¹⁴=chlorine, R¹⁵, R¹⁷=hydrogen, R¹⁶=methylsulfonyloxy, R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Cf.1 to I-Cf.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-D preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Da (≡I where R¹=II-D, R¹⁸, R²⁰=hydrogen, R¹⁹=trifluoromethyl, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Da.1 to I-Da.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-D preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Db (≡I where R¹=II-D, R¹⁸, R²⁰=hydrogen, R¹⁹=trifluoromethyl, R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Db.1 to I-Db.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-D preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Dc (≡I where R¹=II-D, R¹⁸=methyl, R¹⁹=trifluoromethyl, R²⁰=hydrogen, R²=F, R³=Cl; R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Dc.1 to I-Dc.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-D preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Dd (≡I where R¹=II-D, R¹⁸=methyl, R¹⁹=trifluoromethyl, R²⁰=hydrogen; R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Dd.1 to I-Dd.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-D preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-De (≡I where R¹=II-D, R¹⁸=amino, R¹⁹=methylsulfonyl, R²⁰=hydrogen; R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-De.1 to I-De.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-D preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Df (≡I where R¹=II-D, R¹⁸=amino, R¹⁹=methylsulfonyl, R²⁰=hydrogen, R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Df.1 to I-Df.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ea (≡I where R¹=II-E, R²¹=chlorine, R²²=trifluoromethyl, R²³=methyl, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ea.1 to I-Ea.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Eb (≡I where R¹=II-E, R²¹=bromine, R²²=trifluoromethyl, R²³=methyl, R²=Cl, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Eb.1 to I-Eb.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ec (≡I where R¹=II-E, R²¹=chlorine, R²²=trifluoromethyl, R²³=methyl; R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ec.1 to I-Ec.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ed (≡I where R¹=II-E, R²¹=chlorine, R²²=difluoromethoxy, R²³=methyl, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ed.1 to I-Ed.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ee (≡I where R¹=II-E, R²¹=chlorine, R²²=difluoromethoxy, R²³=methyl, R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ee.1 to I-Ee.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ef (≡I where R¹=II-E, R²¹=bromine, R²²=difluoromethoxy, R²³=methyl, R²=Cl, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ef.1 to I-Ef.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Eg (≡I where R¹=II-E, R²¹=chlorine, R²²=methylsulfonyl, R²³=methyl; R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Eg.1 to I-Eg.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-E preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Eh (≡I where R¹=II-E, R²¹=bromine, R²²=methylsulfonyl, R²³=methyl, R²=Cl, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Eh.1 to I-Eh.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-F preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Fb (≡I where R¹=II-F, R²⁴=difluoromethyl, R²⁵=methyl, R²=Cl, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Fb.1 to I-Fb.600 in which the variables R⁴ R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-F preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Fb (≡I where R¹=II-E, R²⁴=difluoromethyl, R²⁵=methyl, R²=Cl, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Fb.1 to I-Fb.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-F preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Fc (≡I where R¹=II-F, R²⁴, R²⁵=(CH₂)₄, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Fc.1 to I-Fc.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-F preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Fd (≡I where R¹=II-F, R²⁴, R²⁵=(CH₂)₄, R²=Cl, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Fd.1 to I-Fd.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-G preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ga (≡I where R¹=II-G, A¹, A² are each oxygen, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ga.1 to I-Ga.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-G preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Gb (≡I where R¹=II-G, A¹, A² are each oxygen, R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Gb.1 to I-Gb.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-H preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Ha (≡I where R¹=II-H, A³ and A⁴ are each oxygen, R²⁶=difluoromethyl, R²⁷=methyl; R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Ha.1 to I-Ha.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-H preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Hb (≡I where R¹=II-H, A³ and A⁴ are each oxygen, R²⁶ and R²⁷ together are tetramethylene, R²=F, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Hb.1 to I-Hb.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

Among the compounds I-H preference is given to the 3-heterocyclyl-substituted benzoic acid derivatives of the formula I-Hc (≡I where R¹=II-H, A³ and A⁴ are each oxygen, R²⁶ and R²⁷ together are tetramethylene, R²=H, R³=Cl, R⁶=H, X=O) in which R⁴, R⁵, R⁷ and R⁸ have the meanings mentioned above, in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds I-Hc.1 to I-Hc.600 in which the variables R⁴, R⁵, R⁷ and R⁸ together have the meanings given in one row of Table 1.

The 3-heterocyclyl-substituted benzoic acid derivatives according to the invention can be prepared similarly to known processes. If no targeted synthesis of the isolation of pure isomers is carried out, the product may be obtained as a mixture of isomers. The mixtures can, if desired, be separated into the substantially pure isomers using methods customary for this purpose such as crystallization or chromatography, including chromatography on an optically active adsorbate. Pure optically active isomers can also be prepared, for example, from appropriate optically active starting materials.

In general, the 3-heterocyclyl-substituted compounds of the formula I are prepared by reacting a 3-heterocyclyl-substituted benzoic acid derivative of the formula III

where R¹, R², R³, R⁴, R⁵ and X are as defined above, if appropriate in the presence of a coupling agent, or by reacting the acid halide which corresponds to III, with a sulfamide of the formula IV

where R⁶, R⁷ and R⁸ are as defined above. Processes for activating carboxylic acids are known, for example, from Houben-Weyl, Methoden der organischen Chemie [Methods of organic chemistry], Vol. E5 (1985), part 1, p. 587 ff. and Vol. E5 (1985), part II, p. 934 ff. The reaction of activated carboxylic acids III or carbonyl halides of III can be carried out analogously to the preparation of carboxylsulfamides described in WO 01/83459, for example in the manner described on p. 31 f.

Preferably, the carboxylic acid III is initially activated by reaction with a coupling agent. The activated carboxylic acid III is then, generally without prior isolation, reacted with the sulfamide IV. Suitable coupling agents are, for example, N,N′-carbonyldiimidazole or carbodiimides, such as dicyclohexylcarbodiimide. These are generally employed in at least equimolar amount and up to a fourfold excess, based on the carboxylic acid III. If appropriate, the resulting reaction mixture of carboxylic acid III and coupling agent is heated and then allowed to cool to room temperature. The reaction is usually carried out in a solvent. Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride or 1,2-dichloroethane, ethers, for example dialkyl ethers such as diethyl ether or methyl tert-butyl ether, or cyclic ethers, such as tetrahydrofuran or dioxane, carboxamides, such as dimethylformamide, N-methyllactams, such as N-methylpyrrolidone, nitriles, such as acetonitrile, aromatic hydrocarbons, such as toluene, aromatic amines, such as pyridine, or mixtures of these. This is followed by addition of the sulfamide IV. In general, the sulfamide IV is dissolved in the solvent which is also used for activating the carboxylic acid.

Alternatively, the carboxylic acid III can also initially be converted into the acid halide which corresponds to III, by using an inorganic acid halide, preferably by using an acid chloride such as thionyl chloride, phosphoryl chloride, phosphorus pentachloride, oxalyl chloride or phosphorus trichloride, and the acid halide formed is, if appropriate, isolated and then reacted with the sulfamide IV. If required, the reactivity of the thionyl chloride is increased by adding catalytic amounts of dimethylformamide. The halogenating agent is usually employed in at least equimolar amount, based on the carboxylic acid. The reaction partner thionyl chloride, phosphorus trichloride or phosphoryl chloride may simultaneously act as solvent. Suitable solvents are furthermore solvents which are inert under the reaction conditions, for example chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons, such as benzene or toluene, aliphatic and cycloaliphatic hydrocarbons, such as hexane, petroleum ether and cyclohexane, and mixtures thereof. The reaction temperature is generally between room temperature and the boiling point of the solvent. After the reaction has ended, excess halogenating agent is generally removed. The resulting acid chloride of III is then reacted with the sulfamide IV. In general, the sulfamide IV is dissolved in the solvent which was also used for preparing the carbonyl halide, unless the solvent is one of the acid halides mentioned above.

It is, of course, also possible to use other methods for activating the carboxylic acid. Such methods are described in the prior art.

The molar ratio of carboxylic acid III or the activated carboxylic acid which corresponds to III or of the acid chloride which corresponds to III to the sulfamide IV is generally at least 0.9:1, preferably at least 1:1. If appropriate, it may also be advantageous to employ a slight excess of sulfamide IV, for example in excesses up to 30%, based on the carboxylic acid III.

The reaction is usually carried out in the presence of a base which is preferably employed in an equimolar amount or an up to fourfold excess, based on the carboxylic acid III. Suitable bases are, for example, amines, such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), pyridine or triethylamine. If appropriate, it may be advantageous to carry out the reaction in the presence of a catalytic amount of 4-dimethylaminopyridine (DMAP). The added base is generally 5-10 mol %, based on the activated carboxylic acid III.

In general, the reaction temperature is in the range from 0° C. to the boiling point of the reaction mixture. Work-up can be carried out in a manner known per se.

The compounds of the formula IV can be obtained by processes known per se, for example by the processes described by G. Hamprecht in Angew. Chem. 93 (1981), 151-163 or by the processes described in WO 01/83459, DE 102 21 910.9 or in Houben-Weyl, Vol. E11 (1985), p. 1019.

3-Heterocyclyl-substituted benzoic acid derivatives of the formula III are known in the prior art or can be prepared similarly to known processes, frequently from the esters that correspond to III.

In this case, the esters are converted into the corresponding carboxylic acids III according to known processes by hydrolysis in acidic media using strong mineral acids, such as concentrated hydrochloric acid or sulfuric acid, or organic acids, such as glacial acetic acids, or mixtures thereof. Alternatively, esters can also be hydrolyzed in an alkaline media using bases such as alkali metal hydroxides, for example sodium hydroxide or potassium hydroxide in the presence of water.

Solvents suitable both for the acid- and the base-catalyzed hydrolysis of esters include, for example, chlorinated aliphatic or alicyclic hydrocarbons, such as methylene chloride or 1,2-dichloroethane, or alcohols. In the case of the acid-catalyzed hydrolysis, the reaction partner usually simultaneously acts as solvent and is therefore employed in excess, based on the ester. The reaction temperature is usually between room temperature and the boiling point of the solvent.

Esters of the carboxylic acid III where R¹ is a heterocyclic radical of the formula II-A are known, for example, from U.S. Pat. No. 6,207,830 and DE 197 41 411. Esters of carboxylic acids of the formula III where R¹ is a heterocyclic radical of the formula II-C are known from WO 97/11059. Esters of carboxylic acids of the formula III where R¹ is a radical II-E are known, for example, from WO 92/06962 and JP 09059113. Esters of carboxylic acids of the formula II-F are known, for example, from JP 61069776. Compounds III which are not explicitly described in these publications can be prepared similarly to these processes.

If the esters of carboxylic acids of the formula III are not known, they can be prepared, for example, by reacting a 3-heterocyclyl-substituted benzoic acid of the formula V

where R¹, R² and R³ are defined above with an α-aminocarboxylic acid ester or an α-hydroxycarboxylic acid ester of the formula VI HXC(R⁴)(R⁵)COOR′  (VI) where X, R⁴ and R⁵ are as defined above and R′ is lower alkyl, in the presence of a dehydrating agent, such as N,N′-carbonyldiimidazole or dicyclohexylcarbodiimide. Alternatively, it is also possible to initially convert the benzoic acid of the formula V into its acid halide, followed by reaction with the compound of the formula VI.

The reaction conditions correspond substantially to the conditions mentioned above for the reaction of III with IV. The reaction is usually carried out in a solvent. Suitable solvents are chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, or mixtures of these. The reaction with a compound of the formula VI is usually carried out at a temperature between room temperature and the boiling point of the solvent. The resulting ester of III is then hydrolyzed, giving the desired 3-heterocyclyl-substituted carboxylic acid III. With respect to the practice of the hydrolysis, reference is made to what was said above.

The carboxylic acid V can be prepared, for example, according to WO 01/083459 or the prior art cited therein, or similarly to the processes described therein. If appropriate, the ester described in the prior art has to be converted by known methods into the carboxylic acid V. With respect to the acid- or base-catalyzed hydrolysis of esters, reference is made to what was said above. The following publications are expressly referred to:

WO 88/10254, WO 89/02891, WO 89/03825, WO 91/00278 (compounds of the formula V or their esters where R¹ is a heterocyclic radical of the formula II-A), EP 0 584 655, WO 00/050409 (the esters of the compounds of the formula V where R¹ is a heterocyclic radical of the formula II-B), WO 96/39392, WO 97/07104 (compounds of the formula V and/or the ester corresponding to V, where R¹ is a heterocyclic radical of the formula II-D), WO 92/06962 (compounds of the formula V where R¹ is a heterocyclic radical of the formula II-E).

The compounds I and their agriculturally useful salts are suitable—both as isomer mixtures and in the form of the pure isomers—as herbicides. Herbicides containing I permit very good control of plant growth on uncultivated areas. In crops such as wheat, rice, corn, soybean and cotton, they are effective against broad-leaved weeds and harmful grasses without significantly damaging the crops. This effect occurs in particular at low application rates.

Depending on the particular application method, the compounds I or the herbicidal compositions comprising them may be used in a further number of crops for eliminating unwanted plants. Suitable are, for example, the following crops:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

The compounds I may also be used in crops which are tolerant to the action of herbicides as a result of breeding, including the use of genetic engineering methods.

Furthermore, the compounds I and their agriculturally useful salts are suitable for the desiccation and/or defoliation of plants.

As desiccants, they are particularly suitable for drying out the above-ground parts of crops, such as potatoes, rape, sunflower and soybeans. This permits completely mechanical harvesting of these important crops.

Also of commercial interest is

-   -   the concentrated dropping of fruits or the reduction of their         adhesion to the plant, for example, in the case of citrus         fruits, olives or other species and varieties of pomes, drupes         and hard-shelled fruit, since because of this, the harvesting of         these fruits is made easier, and     -   the controlled defoliation of useful plants, in particular         cotton.

The dropping brought about by the use of novel active compounds of the formula I depends on the formation of abscission tissue between fruit or leaf part, and shoot part of the plants.

The defoliation of cotton is of very particular commercial interest, since it makes the harvest easier. At the same time, the shortening of the period in which the individual plants ripen leads to an improved quality of the harvested fiber material.

The compounds I or the herbicidal compositions comprising them can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, broadcasting agents or granules, by spraying, nebulizing, dusting, broadcasting or pouring, or for seed dressing or mixing with the seed. The application forms depend on the intended uses; they should in any case ensure very fine distribution of the active ingredients according to the invention.

The herbicides contain a herbicidally effective amount of at least one active compounds of the formula I and auxiliaries which are usually used in formulating crop protection agents.

Suitable inert auxiliaries are essentially:

mineral oil fractions having a medium to high boiling point, such as kerosine and diesel oil, and coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, alkylated benzenes and derivatives thereof, alcohols, such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones, such as cyclohexanone, and strongly polar solvents, for example amines, such as N-methylpyrrolidone, and water.

Aqueous application forms can be prepared from emulsion concentrates, from suspensions, pastes, wettable powders or water-dispersible granules by adding water. For the preparation of emulsions, pastes or oil dispersions, the 3-heterocyclyl-substituted benzoic acid derivatives I, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, adherents, dispersants or emulsifiers. However, it is also possible to prepare concentrates which consist of active ingredients, wetting agents, adherents, dispersants or emulsifiers and possibly solvent or oil, which are suitable for dilution with water.

Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g. lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and fatty acids, alkylsulfonates and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Powders, broadcasting agents and dusting agents can be prepared by mixing or milling the active ingredients together with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetable products, such as grain flour, bark meal, wood meal and nutshell meal, cellulosic powders and other solid carriers.

The concentrations of the active ingredients I in the ready-to-use formulations may be varied within wide ranges. In general, the formulations contain from about 0.001 to 98, preferably from 0.01 to 95, % by weight of at least one active ingredient I. The active ingredients are used in a purity of from 90 to 100%, preferably from 95 to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated, for example, as follows:

-   I. 20 parts by weight of a compound I are dissolved in a mixture     which consists of 80 parts by weight of alkylated benzene, 10 parts     by weight of the adduct of from 8 to 10 mol of ethylene oxide with     1-mol of N-monoethanololeamide, 5 parts by weight of the calcium     salt of dodecylbenzenesulfonic acid and 5 parts by weight of the     adduct of 40 mol of ethylene oxide with 1 mol of castor oil. By     pouring the solution into 100,000 parts by weight of water and     finely distributing it therein, an aqueous dispersion which contains     0.02% by weight of the active ingredient is obtained. -   II. 20 parts by weight of a compound I are dissolved in a mixture     which consists of 40 parts by weight of cyclohexanone, 30 parts by     weight of isobutanol, 20 parts by weight of the adduct of 7 mol of     ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight     of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil.     By pouring the solution into 100,000 parts by weight of water and     finely distributing it therein, an aqueous dispersion which contains     0.02% by weight of the active ingredient is obtained. -   III. 20 parts by weight of a compound I are dissolved in a mixture     which consists of 25 parts by weight of cyclohexanone, 65 parts by     weight of a mineral oil fraction boiling within the range from 210     to 280° C. and 10 parts by weight of the adduct of 40 mol of     ethylene oxide with 1 mol of castor oil. By pouring the solution     into 100,000 parts by weight of water and finely distributing it     therein, an aqueous dispersion which contains 0.02% by weight of the     active ingredient is obtained. -   IV. 20 parts by weight of a compound I are thoroughly mixed with 3     parts by weight of the sodium salt of     diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the     sodium salt of a lignosulfonic acid obtained from a sulfite waste     liquor and 60 parts by weight of silica gel powder, and the mixture     is milled in a hammer mill. By finely distributing the mixture in     20,000 parts by weight of water, a spray liquor which contains 0.1%     by weight of the active ingredient is obtained. -   V. 3 parts by weight of a compound I are mixed with 97 parts by     weight of finely divided kaolin. A dusting agent which contains 3%     by weight of the active ingredient is obtained in this manner. -   VI. 20 parts by weight of a compound I are thoroughly mixed with 2     parts by weight of the calcium salt of dodecylbenzenesulfonic acid,     8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by     weight of sodium salt of a phenol/urea/formaldehyde condensate and     68 parts by weight of a paraffinic mineral oil. A stable oily     dispersion is obtained. -   VII. 1 part by weight of a compound I is dissolved in a mixture     which consists of 70 parts by weight of cyclohexanone, 20 parts by     weight of ethoxylated isooctylphenol and 10 parts by weight of     ethoxylated castor oil. A stable emulsion concentrate is obtained. -   VIII. 1 part by weight of a compound I is dissolved in a mixture     which consists of 80 parts by weight of cyclohexanone and 20 parts     by weight of Wettol® EM31 (=nonionic emulsifier based on ethoxylated     castor oil; BASF AG). A stable emulsion concentrate is obtained.

The active compounds I or the herbicidal compositions can be applied by the preemergence or postemergence method. The herbicidal compositions or active compounds can also be applied by sowing crop seed which has been pretreated with the herbicidal compositions or active compounds. If the active ingredients are less well tolerated by certain crops, it is possible to use application methods in which the herbicides are sprayed with the aid of the sprayers in such a way that the leaves of the sensitive crops are as far as possible not affected, while the active compounds reach the leaves of undesirable plants growing underneath or the uncovered soil surface (post-directed, lay-by).

The application rates of active compound I are from 0.001 to 3.0, preferably from 0.01 to 1.0, kg/ha of active ingredient (a.i.), depending on the aim of control, the season, the target plants and the state of growth.

In order to broaden the action spectrum and to achieve synergistic effects, the 3-heterocyclyl-substituted benzoic acid derivatives I may be mixed with many members of other groups of herbicidal or growth-regulating active ingredients and applied together with them.

Examples of suitable components of the mixture are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, aryloxy-/hetaryloxyalkanoic acids and derivatives thereof, benzoic acid and derivatives thereof, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanediones, hetarylarylketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives, carbamates, quinolinecarboxylic acid and derivatives thereof, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and derivatives thereof, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and derivatives thereof, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid and derivatives thereof, 2-phenylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and derivatives thereof, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolcarboxamides and uracils.

It may also be useful to apply the compounds I together, alone or in combination with other herbicides, also as a mixture with further crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. The miscibility with mineral salt solutions which are used for eliminating nutrient and trace element deficiencies is also of interest. Nonphytotoxic oils and oil concentrates can also be added.

The examples below are intended to illustrate the invention without limiting it.

PREPARATION EXAMPLES Example 1 (S)-2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoro methyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]propionic acid N,N-dimethylsulfamide (S-enantiomer of compound I-Aa. 242)

1.1: 2-Chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoic acid

13.9 g (34 mmol) of isopropyl 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoate (CAS No. 105756-82-9, U.S. Pat. No. 5,176,735, U.S. Pat. No. 4,943,309, WO 88/10254) were dissolved in 100 ml of glacial acetic acid and 100 ml of conc. HCl, and the mixture was heated at 70° C. for 15 hours. The acetic acid was removed under reduced pressure, the residue was taken up in water and the resulting precipitate was filtered off with suction. Drying gave 11.3 g of the uracilcarboxylic acid which was used for the next step without further purification.

¹H-NMR (DMSO-d₆) δ (ppm)=8.1 (d, 1H), 7.8 (d, 1H), 6.6 (s, 1H), 3.4 (s, 3H).

1.2: Methyl (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoro methyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]propionate

5.0 g (13.64 mmol) of uracilcarboxylic acid from 1.1 in 50 ml of thionyl chloride were heated at reflux for 3 h, and unreacted thionyl chloride was then removed under reduced pressure. The resulting acid chloride was then dissolved in 50 ml of methylene chloride, and the resulting solution was, at 0-5° C., added dropwise with stirring to a solution of 1.6 g (15.01 mmol) of methyl (S)-lactate, 0.2 g (1.36 mmol) of 4-dimethylaminopyridine (DMAP) and 1.7 g (16.37 mmol) of triethylamine in 80 ml of CH₂Cl₂. The mixture was allowed to warm to room temperature and stirred at room temperature for another 16 hours. The reaction mixture was then concentrated and chromatographed on silica gel using cyclohexane/ethyl acetate 70/30. The solvent was evaporated under reduced pressure, giving 5.85 g of the ester.

¹H-NMR (DMSO-d₆) δ (ppm)=8.0 (d, 1H), 7.4 (d, 1H), 6.4 (s, 1H), 5.4 (q, 1H), 4.8 (s, 3H), 3.6 (s, 3H), 1.5 (d, 3H).

1.3: (S)-2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]propionic acid

25 ml of glacial acetic acid and 25 ml of conc. HCl were added to 3.6 g (8 mmol) of the ester from 1.2, the mixture was heated at 60° C. for 4 hours and then stirred at room temperature for 8 hours. The acetic acid was removed under reduced pressure and the reaction mixture was diluted with water and extracted three times with in each case about 150 ml of ethyl acetate. The combined organic phases were then dried over Na₂SO₄ and concentrated under reduced pressure, giving 3.3 g of acid.

¹H-NMR (DMSO-d₆) δ (ppm)=8.0 (d, 1H), 7.4 (d, 1H), 6.4 (s, 1H), 5.4 (q, 1H), 3.5 (s, 3H), 1.6 (d, 3H).

1.4: (S)-2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]propionic acid N,N-dimethylsulfamide

0.45 g (1.03 mmol) of the acid from 1.3 in 10 ml of thionyl chloride was heated at reflux for 3 hours and excess thionyl chloride was then removed under reduced pressure and the resulting acid chloride was dissolved in about 5 ml of CH₂Cl₂. This solution was, at about 5° C., added dropwise to a solution of 0.13 g (1.03 mmol) of N,N-dimethylsulfamide, 0.23 g (2.23 mmol) of triethylamine and a catalytic amount of DMAP in 20 ml of CH₂Cl₂. The reaction mixture was stirred at room temperature for 14 hours and then concentrated under reduced pressure. The residue was taken up in ethyl acetate and washed with about 200 ml of 10% strength hydrochloric acid. Chromatography on silica gel using cyclohexane/ethyl acetate 70/30 gave 0.16 g of the title compound of m.p. 207-208° C.

¹H-NMR: see Table 2

Example 2 2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoro-methyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]-2-methyl-propionic acid N-methyl-N-allylsulfamide (compound I-Ab.465)

0.33 g (2.2 mmol) of N-methyl-N-allylsulfamide, 0.27 g of 4-dimethylaminopyridine and 0.64 ml of triethylamine were dissolved in 10 ml of dichloromethane. A solution of 0.98 g (2.2 mmol) of 2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoro-methyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]-2-methyl-propionyl chloride (CAS No. 160152-72-7) in dichloromethane was then added dropwise. The solution was stirred for 3 days and then concentrated, and the residue was taken up in ethyl acetate. The organic phase was washed with 10% strength hydrochloric acid and water and dried over sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 2:1) gave 0.21 g of the title compound of melting point 161-164° C.

Example 3 (S)-2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoro-methyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionic acid N-methyl-N-allylsulfamide (S enantiomer of compound I-Ab.265) 3.1: Methyl (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoro-methyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionate

7.0 g (20 mmol) of 2-chloro-5-(3-methyl-2,6-dioxo-4-tri-fluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoic acid (CAS No. 120890-58-6) were dissolved in 50 ml of thionyl chloride. The reaction mixture was then heated under reflux for 3 hours, and the resulting solution of the acid chloride was concentrated. 2.3 g (22 mmol) of methyl (S)-lactate, 2.46 g (20 mmol) of 4-dimethylaminopyridine and 2.44 g (20 mmol) of triethylamine were then dissolved in 50 ml of dichloromethane, and a solution of the acid chloride obtained above in dichloromethane was then added dropwise at 0° C. The reaction mixture was stirred at room temperature for 16 hours, and the solution was then concentrated. Column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 2:1) gave 7.0 g of methyl (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-di-hydro-2H-pyrimidin-1-yl)benzoyloxy]propionate of melting point 59-60° C.

3.2: (S)-2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionic acid

7.0 g (16 mmol) of methyl (S)-2-[2-chloro-5-(3-methyl-2,6-di-oxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyl-oxy]propionate from example 3.1 were dissolved in 50 ml of acetic acid, 50 ml of conc. hydrochloric acid were added and the solution was heated under reflux for 4 hours. Most of the acetic acid was distilled off, and the solution that remained was poured onto ice-water. The aqueous phase was extracted three times with ethyl acetate, the organic phase was dried over sodium sulfate, the drying agent was filtered off and the filtrate was concentrated to dryness, which gave 5.7 g of (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionic acid.

3.3: (S)-2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionyl chloride

5.7 g (14 mmol) of (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]-propionic acid from example 3.2 were dissolved in 50 ml of thionyl chloride, and the reaction mixture was heated under reflux for 3.5 hours. The solution was allowed to cool and concentrated, which gave 5.9 g of (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-benzoyloxy]propionyl chloride.

3.4: (S)-2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionic acid N-methyl-N-allylsulfamide

0.33 g (2.2 mmol) of N-methyl-N-allylsulfamide, 0.27 g of 4-dimethylaminopyridine and 0.67 ml of triethylamine were dissolved in 10 ml of dichloromethane, and a solution of 0.98 g (2.2 mmol) of (S)-2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoro-methyl-3,6-dihydro-2H-pyrimidin-1-yl)benzoyloxy]propionyl chloride from example 3.3 in 10 ml of dichloromethane was added dropwise. The solution was stirred for 16 hours and then concentrated, and the resulting residue was dissolved in ethyl acetate. The organic phase was washed with 10% strength hydrochloric acid and water and dried over sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Column chromatography on silica gel gave 0.26 g of the title compound.

Example 4 2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]-2-methyl-propionic acid N,N-dimethyl-N-allylsulfamide (compound I-Aa.442) 4.1: Methyl 2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoro-methyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]-2-methylpropionate

0.61 g (5.2 mmol) of methyl 2-hydroxy-2-methylpropionate, 70 mg (0.5 mmol) of 4-N-pyrrolidinopyridine and 0.87 ml (6.2 mmol) of triethylamine were dissolved in 50 ml of tetrahydrofuran, and a solution of 2 g (5.2 mmol) of the acid chloride from example 1.2 in 50 ml of tetrahydrofuran were then added dropwise. The solution was stirred for 16 hours and then concentrated, and the residue was then dissolved in ethyl acetate. The organic phase was washed with 10% strength citric acid and water and dried over sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 2:1) gave 1.0 g of methyl 2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]-2-methyl-propionate.

4.2: 2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]-2-methyl-propionic acid

1.0 g (2.1 mmol) of methyl 2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluoro-benzoyloxy]-2-methylpropionate from example 4.1 was dissolved in 50 ml of acetic acid, 50 ml of conc. hydrochloric acid were added and the reaction mixture was heated under reflux for 5 hours. Most of the acetic acid was distilled off, and the solution that remained was poured into ice-water. The precipitate was filtered off and dried, which gave 0.65 g of 2-[2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]-2-methylpropionic acid.

4.3: 2-[2-Chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-di-hydro-2H-pyrimidin-1-yl)-4-fluorobenzoyloxy]-2-methylpropionic acid N,N-dimethylsulfamide

0.65 g (1.4 mmol) of 2-[(2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimdin-1-yl)-4-fluorobenzoyloxy]-2-methylpropionic acid from example 4.2 was dissolved in 30 ml of thionyl chloride, the reaction mixture was heated under reflux for 3 hours and the resulting solution of the acid chloride was then concentrated. 0.18 g (1.4 mmol) of N,N-dimethylsulfamide, 0.07 g (1.4 mmol) of 4-dimethylaminopyridine and 0.35 ml (3.5 mmol) of triethylamine were dissolved in 10 ml of dichloromethane, and a solution of the acid chloride which had been prepared beforehand in 10 ml of dichloromethane was then added dropwise. The solution was stirred for 16 hours and then concentrated, and the residue was then dissolved in ethyl acetate. The organic phase was washed with 10% strength hydrochloric acid and water, the organic phase was dried over sodium sulfate, the drying agent was filtered off and the filtrate was concentrated. Column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 2:1) gave 0.30 g of the title compound of melting point 211-213° C.

In addition to the benzoic acid derivatives of the formula I described above, Table 2 below lists further compounds of the formula I which were prepared analogously.

TABLE 2 No. ¹H-NMR δ [ppm], m.p. [° C.] S-enantiomer (CDCl₃): 8.7(br., 1H), 8.0(m, 1H), 207–208 of 7.5(d, 1H), 6.4(s, 1H), 5.4(m, 1H), the 3.5(s, 3H), 2.9(s, 6H), 1.6(d, 3H). compound I-Aa.242 S-enantiomer (CDCl₃): 8.7(br., 1H), 8.0(m, 1H), 170–171 of 7.5(d, 1H), 6.4(s, 1H), 5.4(m, 1H), the 3.5(s, 3H), 3.4(q, 2H), 2.9(s, 3H), compound 1.6(d, 3H), 1.3(t, 3H), I-Aa.243 S-enantiomer (CDCl₃): 8.7(br., 1H), 8.0(m, 1H), 164–165 of 7.5(d, 1H), 6.4(s, 1H), 5.4(m, 1H), the 4.2(m, 1H), 3.5(s, 3H), 2.9(s, 3H), compound 1.6(d, 3H), 1.3(d, 6H). I-Aa.246 S-enantiomer (CDCl₃): 8.7(br., 1H), 8.0(m, 1H), 132–134 of 7.5(d, 1H), 6.4(s, 1H), 5.4(m, 1H), the 3.6–3.4(m, 7H), 3.3(s, 3H), 2.9(s, compound 3H), 1.6(d, 3H). I-Aa.251 S-enantiomer (CDCl₃): 8.7(br., 1H), 8.0(m, 1H), 129–130 of 7.5(d, 1H), 6.4(s, 1H), 5.9–5.8(m, 1H), the 5.5–5.1(m, 3H), 3.9(d, 1H), 3.5(s, 3H), compound 2.9(s, 3H), 1.6(d, 3H). I-Aa.265 S-enantiomer (CDCl₃): 8.7(br., 1H), 8.0(m, 1H), of 7.5(d, 1H), 6.4(s, 1H), 5.4(m, 1H), the 4.2(m, 2H), 3.5(s, 3H), 2.9(s, 3H), compound 2.3(m, 1H), 1.6(d, 3H). I-Aa.269 I-Ab.465 (DMSO-d₆): 11.7(br. s, 1H), 7.9(m, 1H), 161–164 7.7(m, 1H), 7.6(m, 1H), 6.6(s, 1H), 5.8(m, 1H), 5.3–5.2(m, 2H), 3.8(d, 2H), 3.4(s, 3H), 2.8(s, 3H), 1.6(s, 6H). I-Ab.469 (DMSO-d₆): 11.7(br. s, 1H), 7.9(m, 1H), 7.7(m, 1H), 7.6(m, 1H), 6.6(s, 1H), 4.1(d, 2H), 3.4(s, 3H), 3.3(t, 3H), 2.8(s, 3H), 1.6(s, 6H). I-Ab.442 (DMSO-d₆): 11.7(br. s, 1H), 7.9(m, 1H), 7.7(m, 1H), 7.6(m, 1H), 6.6(s, 1H), 4.0(m, 1H), 3.4(s, 3H), 2.8(s, 6H), 1.6(s, 6H). S-enantiomer oil of compound I-Ab.248 S-enantiomer oil of compound I-Ab.242 S-enantiomer oil of compound I-Ab.243 S-enantiomer oil of compound I-Ab.265 I-Ab.443 193–194 I-Ab.446 177–179 I-Ab.448 140–142 I-Aa.442 (DMSO-d₆): 11.63(s, 1H), 8.13(d, 1H), 211–213 7.91(d, 1H), 6.63(s, 1H), 3.42(s, 3H), 2.84(s, 6H), 1.61(s, 6H)

Use Examples

The herbicidal activity of the 3-heterocyclyl-substituted benzoic acid derivatives I was demonstrated by the following greenhouse experiments:

The cultivation containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

For the preemergence treatment, directly after sowing the active compounds, which had been suspended or emulsified in water, were applied by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this was adversely affected by the active compounds.

For the postemergence treatment, the test plants were first grown to a height of 3-15 cm, depending on the plant habit, and only then treated with the active compounds which had been suspended or emulsified in water. The test plants were for this purpose either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to the treatment. The application rate for the postemergence treatment was 7.8 or 3.9 g of a.i. (active ingredient)/ha.

Depending on the species, the plants were kept at 10-25° C. or 20-35° C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

Evaluation was carried out using a scale from 0.0 to 100. 100 means no emergence of the plants, or complete destruction of at least the above-ground parts, and 0 means no damage, or normal course of growth.

The plants used in the greenhouse experiments were of the following species:

Scientific name Common name Amaranthus retroflexus redroot pigweed Chenopodium album lambsquarters (goosefoot)

Applied by the postemergence method, the S enantiomer of the compound I-Aa.246 showed excellent herbicidal activity against the abovementioned plants.

Use Examples Desiccant/Defoliant Action

The test plants used were young cotton plants with 4 leaves (without cotyledons) which had been grown under greenhouse conditions (re1. atmospheric humidity 50-70%; day/night temperature 27/20° C.).

The young cotton plants were subjected to foliar treatment to runoff point with aqueous preparations of the active compounds (with addition of 0.15% by weight, based on the spray mixture, of the fatty alcohol alkoxylate Plurafac® LF 700¹)). The amount of water applied was 1000 l/ha (converted). After 13 days, the number of leaves shed and the degree of defoliation in % were determined. 1) a low-foam, nonionic surfactant from BASF AG

The untreated control plants did not shed any leaves. 

1. A 3-heterocyclyl-substituted benzoic acid compound of the formula I

wherein: X is oxygen or NR⁹, R¹ is a heterocyclic radical of the formulae II-A to II-D,

R² is hydrogen or halogen, R³ is halogen or cyano, R⁴, R⁵ independently of one another are hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, or R⁴ and R⁵ together are a group ═CH₂, R⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, R⁷, R⁸ independently of one another are hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl, cyano-C₁-C₄-alkyl, C₁-C₄-alkoxycarbonyl-C₁-C₄-alkyl, amino-C₁-C₄-alkyl, C₁-C₄-alkylamino-C₁-C₄-alkyl, di(C₁-C₄-alkyl)amino-C₁-C₄-alkyl, aminocarbonyl-C₁-C₄-alkyl, (C₁-C₄-alkylamino)carbonyl-C₁-C₄-alkyl, di(C₁-C₄-alkyl)aminocarbonyl-C₁-C₄-alkyl, phenyl or C₁-C₄-alkylphenyl or R⁹ is hydrogen, hydroxyl, C₁-C₄-alkyl, C₁-C₄-alkoxy, phenyl, phenyl-C₁-C₄-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, R¹⁰ is hydrogen, C₁-C₄-alkyl or amino, R¹¹ is C₁-C₄-alkyl or C₁-C₄-haloalkyl, R¹² is hydrogen or C₁-C₄-alkyl, R¹³, R^(13′) independently of one another are hydrogen or C₁-C₄-alkyl, R¹⁴ is halogen, R¹⁵ is hydrogen or C₁-C₄-alkyl, R¹⁶ is C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl or C₁-C₄-alkylsulfonyloxy, R¹⁷ is hydrogen or C₁-C₄-alkyl, R¹⁸ is hydrogen, C1-C4-alkyl or amino, R¹⁹ is C₁-C₄-haloalkyl, C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl, R²⁰ is hydrogen or C₁-C₄-alkyl, R²¹ is hydrogen, halogen or C₁-C₄-alkyl, or an agriculturally useful salt thereof.
 2. A benzoic acid compound as claimed in claim 1 where R² is fluorine, chlorine or hydrogen.
 3. A benzoic acid compound as claimed in claim 1 where R³ is chlorine or cyano.
 4. A benzoic acid compound as claimed in claim 1 where X is oxygen.
 5. A benzoic acid compound as claimed in claim 1 where R⁶ is hydrogen.
 6. A benzoic acid compound as claimed in claim 1 where R¹ is a heterocyclic radical of the formula II-A in which R¹⁰ is C₁-C₄-alkyl or amino, R¹¹ is C₁-C₄-haloalkyl and R¹² is hydrogen.
 7. A benzoic acid compound as claimed in claim 1 where R¹ is a heterocyclic radical of the formula II-B in which R¹³ and R^(13′) are each independently of one another C₁-C₄-alkyl.
 8. A benzoic acid compound as claimed in claim 1 where R¹ is a heterocyclic radical of the formula II-C in which R¹⁴ is fluorine or chlorine, R¹⁵ is hydrogen and R¹⁶ is C₁-C₄-haloalkyl, C₁-C₄-alkylsulfonyl or C₁-C₄-alkylsulfonyloxy.
 9. A benzoic acid compound as claimed in claim 1 where R1 is a heterocyclic radical of the formula II-D in which R¹⁸ is hydrogen, methyl or amino, R¹⁹ is C₁-C₄-haloalkyl or C₁-C₄-alkylsulfonyl and R¹⁹ is hydrogen.
 10. A benzoic acid compound as claimed in claim 1 where R² is hydrogen, chlorine or fluorine, R³ is chlorine or cyano, R⁶ is hydrogen and X is oxygen.
 11. A benzoic acid compound as claimed in claim 1 where R⁴ or R⁵ is hydrogen and the other radical R⁴ or R⁵ is C₁-C₄-alkyl or R⁴, R⁵ are each methyl.
 12. A composition comprising a herbicidally effective amount of at least one 3-heterocyclyl-substituted benzoic acid compound of the formula I or an agriculturally useful salt thereof as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.
 13. A composition for the desiccation/defoliation of plants, comprising an effective amount of at least one 3-heterocyclyl-substituted benzoic acid compound of the formula I or an agriculturally useful salt thereof as claimed in claim 1 which acts as a desiccant/defoliant and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.
 14. A method for controlling unwanted vegetation, which comprises applying a herbicidally effective amount of at least one 3-heterocyclyl-substituted benzoic acid compound of the formula I or an agriculturally useful salt thereof as claimed in claim 1 to act on plants, their habitat and/or on seed.
 15. A method for the desiccation/defoliation of plants, which comprises applying an amount which is effective as a desiccant/defoliant of at least one 3-heterocyclyl-substituted benzoic acid compound of the formula I or an agriculturally useful salt thereof as claimed in claim 1 to act on plants.
 16. A method for controlling unwanted vegetation or for the desiccation/defoliation of plants, comprising applying to plants, the habitat of the plants or seeds of the plants an agriculturally effective amount of a compound or salt of claim
 1. 